Fungicidal oxadiazoles

ABSTRACT

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, tautomers, N-oxides, and salts thereof, wherein R 1 , Z 1 , W, Z 2  and J are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling plant disease caused by a fungal pathogen comprising applying an effective amount of a compound or a composition of the invention.

FIELD OF THE INVENTION

This invention relates to certain oxadiazoles, their N-oxides, salts andcompositions, and methods of their use as fungicides.

BACKGROUND OF THE INVENTION

The control of plant diseases caused by fungal plant pathogens isextremely important in achieving high crop efficiency. Plant diseasedamage to ornamental, vegetable, field, cereal, and fruit crops cancause significant reduction in productivity and thereby result inincreased costs to the consumer. Many products are commerciallyavailable for these purposes, but the need continues for new compoundswhich are more effective, less costly, less toxic, environmentally saferor have different sites of action.

PCT Patent Publication WO 2017178549 disclosestrifluoromethyl-oxadiazole derivatives and their use in agriculture.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including allstereoisomers), N-oxides, hydrates (and solvates thereof), and saltsthereof, agricultural compositions containing them and their use asfungicides:

wherein

-   -   R¹ is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆        alkylcarbonyl or C₂-C₆ alkoxycarbonyl, each optionally        substituted with up to 3 substituents independently selected        from R²; or phenyl optionally substituted with up to 3        substituents independently selected from R^(3a); or a 3- to        7-membered nonaromatic carbocyclic ring, wherein up to 3 carbon        atom ring members are independently selected from C(═O) and        C(═S), each ring optionally substituted with up to 3        substituents independently selected from R^(3a); or a 5- to        6-membered heterocyclic ring, each ring containing ring members        selected from carbon atoms and 1 to 4 heteroatoms independently        selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein        up to 3 carbon atom ring members are independently selected from        C(═O) and C(═S), and the sulfur atom ring members are        independently selected from S(═O)_(u)(═NR¹²)_(v), each ring        optionally substituted with up to 5 substituents independently        selected from R^(3a) on carbon atom ring members and R^(3b) on        nitrogen atom ring members;    -   Z¹ is O, —(CH₂)_(n)NR^(4a)−, —(CH₂)_(n)NR^(4a)NR^(4b)— or        —CH═NNR^(4b)—, wherein the bond projecting to the left is        attached to R¹, and the bond projecting to the right is attached        to C═W;    -   W is O or S;    -   Z² is —O(CH₂)_(m)—, —OCH₂CH₂O— or —NR⁵N═CH—, wherein the bond        projecting to the left is attached to C═W, and the bond        projecting to the right is attached to J, each carbon atom        optionally substituted with up to 2 substituents independently        selected from R⁶;    -   J is phenyl optionally substituted with up to 2 substituents        independently selected from R⁷; or a 5- to 6-membered        heteroaromatic ring, each ring containing ring members selected        from carbon atoms and 1 to 4 heteroatoms independently selected        from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2        ring members are independently selected from C(═O), C(═S), S(═O)        and S(═O)₂, each ring optionally substituted with up to 2        substituents independently selected from R⁷ on carbon atom ring        members and R⁸ on nitrogen atom ring members; each R² is        independently halogen, hydroxy, cyano, —S—C≡N, —SH, amino,        nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆        halocycloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio,        C₁-C₄ alkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄        haloalkylsulfonyl, C₁-C₄ alkylamino, C₂-C₄ dialkylamino, C₂-C₄        alkylcarbonyl, C₂-C₄ haloalkylcarbonyl, C₂-C₅ alkoxycarbonyl,        C₂-C₅ haloalkoxycarbonyl, C₂-C₅ alkylaminocarbonyl or C₃-C₅        dialkylaminocarbonyl; or phenyl, pyridinyl, pyrazolyl,        imidazolyl, triazolyl, thiazolyl, oxazolyl, isoxazolyl,        oxetanyl, 1,3-dioxolanyl, tetrahydropyranyl, thienyl, furanyl,        pyrrolidinyl, isoxazolinyl, tetrahydrofuranyl, piperidinyl,        morpholinyl or piperazinyl, each optionally substituted with up        to 3 substituents independently selected from R^(3c) on carbon        atom ring members and R^(3d) on nitrogen atom ring members;    -   each R^(3a) and R^(3c) is independently halogen, hydroxy, cyano,        amino, nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄        alkynyl, C₁-C₄ hydroxyalkyl, C₃-C₆ cycloalkyl, C₄-C₇        cycloalkylalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄        alkenyloxy, C₂-C₄ alkynyloxy, C₂-C₄ alkoxyalkyl, C₂-C₆        alkylcarbonyloxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio, C₂-C₆        alkylcarbonylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylsulfinyl,        C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄        alkylsulfonyloxy, C₁-C₄ alkylamino, C₂-C₈ dialkylamino, C₃-C₆        cycloalkylamino, C₂-C₄ alkylcarbonyl, C₂-C₆ alkoxycarbonyl,        C₂-C₆ alkylaminocarbonyl, C₃-C₈ dialkylaminocarbonyl or C₃-C₆        trialkylsilyl;    -   each R^(3b) and R^(3d) is independently C₁-C₃ alkyl, C₁-C₃        alkoxy, C₂-C₃ alkylcarbonyl or C₂-C₃ alkoxycarbonyl;    -   R^(4a) and R^(4b) are each independently H, hydroxy, cyano,        C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ haloalkenyl,        C₂-C₄ alkynyl, C₂-C₄ haloalkynyl, C₁-C₄ alkoxy, C₁-C₄        haloalkoxy, C₂-C₄ alkoxyalkyl, C₂-C₄ alkylthioalkyl, C₁-C₄        alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, C₂-C₄        alkylsulfinylalkyl, C₂-C₄ alkylsulfonylalkyl, C₂-C₄        alkylcarbonyl, C₂-C₄ haloalkylcarbonyl, C₂-C₅ alkoxycarbonyl,        C₃-C₅ alkoxycarbonylalkyl, C₂-C₅ alkylaminocarbonyl, C₃-C₅        dialkylaminocarbonyl, C₃-C₇ alkylaminocarbonylalkyl or C₄-C₇        dialkylaminocarbonylalkyl; or    -   one pair of R¹ and R^(4a) substituents or one pair of R¹ and        R^(4b) substituents are taken together with the atoms to which        they are attached to form a 5- to 7-membered ring containing        ring members selected from carbon atoms and optionally up to 3        heteroatoms independently selected from up to 1 O, up to 1 S and        up to 2 N atoms, wherein up to 3 ring members are independently        selected from C(═O), C(═S), S(═O) and S(═O)₂, each ring        optionally substituted with up to 4 substituents independently        selected from R⁹; or    -   one pair of R^(3a) and R^(4a) substituents or one pair of R^(3a)        and R^(4b) substituents are taken together with the atoms to        which they are attached to form a 5- to 7-membered ring        containing ring members selected from carbon atoms and        optionally up to 3 heteroatoms independently selected from up to        1 O, up to 1 S and up to 2 N atoms, wherein up to 3 ring members        are independently selected from C(═O), C(═S), S(═O) and S(═O)₂,        each ring optionally substituted with up to 4 substituents        independently selected from R¹⁰; or    -   one pair of R^(3b) and R^(4a) substituents or one pair of R^(3b)        and R^(4b) substituents are taken together with the nitrogen        atoms to which they are attached to form a 5- to 7-membered ring        containing ring members selected from carbon atoms and        optionally up to 3 heteroatoms independently selected from up to        1 O, up to 1 S and up to 2 N atoms, wherein up to 3 ring members        are independently selected from C(═O), C(═S), S(═O) and S(═O)₂,        each ring optionally substituted with up to 4 substituents        independently selected from R¹¹;    -   R⁵ is H, hydroxy, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄        alkenyl, C₂-C₄ haloalkenyl, C₂-C₄ alkynyl, C₂-C₄ haloalkynyl,        C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄ alkoxyalkyl, C₂-C₄        alkylthioalkyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl,        C₂-C₄ alkylsulfinylalkyl, C₂-C₄ alkylsulfonylalkyl, C₂-C₄        alkylcarbonyl, C₂-C₄ haloalkylcarbonyl, C₂-C₅ alkoxycarbonyl,        C₃-C₅ alkoxycarbonylalkyl, C₂-C₅ alkylaminocarbonyl or C₃-C₅        dialkylaminocarbonyl;    -   each R⁶ is independently halogen, hydroxy, cyano, nitro, C₁-C₂        alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy, C₁-C₂ haloalkoxy or C₂-C₄        alkoxyalkyl; or phenyl optionally substituted with up to 3        substituents independently selected from R¹³;    -   each R⁷ is independently halogen, hydroxy, cyano, amino, nitro,        C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl,        C₁-C₄ hydroxyalkyl, C₃-C₆ cycloalkyl, C₄-C₇ cycloalkylalkyl,        C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄ alkenyloxy, C₂-C₄        alkynyloxy, C₂-C₄ alkoxyalkyl, C₂-C₄ alkylcarbonyloxy, C₁-C₄        alkylthio, C₁-C₄ haloalkylthio, C₂-C₄ alkylcarbonylthio, C₁-C₄        alkylsulfinyl, C₁-C₄ haloalkylsulfinyl, C₁-C₄ alkylsulfonyl,        C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylsulfonyloxy, C₁-C₄        alkylamino, C₂-C₆ dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₄        alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl,        C₃-C₆ dialkylaminocarbonyl or C₃-C₆ trialkylsilyl;    -   each R⁸ is independently C₁-C₃ alkyl;    -   each R⁹, R¹⁰ and R¹¹ is independently halogen, hydroxy, cyano,        nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄        haloalkenyl, C₂-C₄ alkynyl, C₂-C₄ haloalkynyl, C₁-C₄ alkoxy,        C₁-C₄ haloalkoxy, C₂-C₄ alkoxyalkyl, C₂-C₄ alkylthioalkyl, C₁-C₄        alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, C₂-C₄        alkylsulfinylalkyl, C₂-C₄ alkylsulfonylalkyl, C₂-C₄        alkylcarbonyl, C₂-C₄ haloalkylcarbonyl, C₂-C₅ alkoxycarbonyl,        C₃-C₅ alkoxycarbonylalkyl, C₂-C₅ alkylaminocarbonyl or C₃-C₅        dialkylaminocarbonyl;    -   each R¹² is independently H, cyano, C₁-C₃ alkyl or C₁-C₃        haloalkyl;    -   each R¹³ is independently halogen, cyano, amino, nitro, C₁-C₄        alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄        hydroxyalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄ alkenyloxy,        C₂-C₄ alkynyloxy or C₂-C₄ alkoxyalkyl;    -   n is 0;    -   m is 1, 2 or 3; and    -   each u and v are independently 0, 1 or 2 in each instance of        S(═O)_(u)(═NR¹²)_(v), provided that the sum of u and v is 0, 1        or 2;

provided that:

-   -   (a) when J is phenyl or a 6-membered heteroaromatic ring, then J        is attached to Z² and the oxadiazole ring in Formula 1 in a        meta- or para-arrangement; and    -   (b) the compound of Formula 1 is not:

-   [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl](2-chlorophenyl)]methyl    N-(phenylmethyl)carbamate;

-   [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl](4-chlorophenyl)]methyl    N-(phenylmethyl)carbamate;

-   [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl] methyl ester    4-morpholinecarboxylic acid;

-   [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl    acetyl(methyl)carbamate;

-   [4-[5-(trifluoromethyl)-1,2-3-oxadiazol-3-yl]phenyl]methyl    N-methylcarbamate;

-   [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl    N-2-pyridinylcarbamate;

-   1-[4-[5-(trifluoromethyl)-1,2,3-oxadiazol-3-yl]phenyl]ethyl    N,N-dimethylcarbamate;

-   [4-[5-(trifluoromethyl)-1,2-3-oxadiazol-3-yl]phenyl]methyl    N-methoxy-N-methylcarbamate;

-   [4-[5-(trifluoromethyl)-1,2-3-oxadiazol-3-yl]phenyl]methyl    N-(2,2,2-trifluoroethyl)carbamate;

-   [4-[5-(trifluoromethyl)-1,2-3-oxadiazol-3-yl]phenyl]methyl    N-cyclopropylcarbamate; or

-   [4-[5-(trifluoromethyl)-1,2-3-oxadiazol-3-yl]phenyl]methyl    N,N-dimethylcarbamate.

More particularly, this invention pertains to a compound of Formula 1(including all geometric and stereoisomers), an N-oxide, a hydrate, or asalt thereof.

This invention also relates to a fungicidal composition comprising (a) acompound of Formula 1; and (b) at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents.

This invention also relates to a fungicidal composition comprising (a) acompound of Formula 1; and (b) at least one other fungicide (e.g., atleast one other fungicide having a different site of action).

This invention further relates to a method for controlling plantdiseases caused by fungal plant pathogens comprising applying to theplant or portion thereof, or to the plant seed, a fungicidally effectiveamount of a compound of the invention (e.g., as a composition describedherein).

This invention also relates to a composition comprising a compound ofFormula 1, an N-oxide, a hydrate, or a salt thereof, and at least oneinvertebrate pest control compound or agent.

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains,” “containing,” “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process or method that comprises alist of elements is not necessarily limited to only those elements butmay include other elements not expressly listed or inherent to suchcomposition, mixture, process or method.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition or method that includes materials, steps, features,components, or elements, in addition to those literally disclosed,provided that these additional materials, steps, features, components,or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in the present disclosure and claims, “plant” includesmembers of Kingdom Plantae, particularly seed plants (Spermatopsida), atall life stages, including young plants (e.g., germinating seedsdeveloping into seedlings) and mature, reproductive stages (e.g., plantsproducing flowers and seeds). Portions of plants include geotropicmembers typically growing beneath the surface of the growing medium(e.g., soil), such as roots, tubers, bulbs and corms, and also membersgrowing above the growing medium, such as foliage (including stems andleaves), flowers, fruits and seeds.

As referred to herein, the term “seedling”, used either alone or in acombination of words means a young plant developing from the embryo of aseed or bud of a vegetative propagation unit such as tuber, corm orrhizome.

As referred to herein, the term “broadleaf” used either alone or inwords such as “broadleaf crop” means dicot or dicotyledon, a term usedto describe a group of angiosperms characterized by embryos having twocotyledons.

As referred to in this disclosure, the terms “fungal pathogen” and“fungal plant pathogen” include pathogens in the Ascomycota,Basidiomycota and Zygomycota phyla, and the fungal-like Oomycota classthat are the causal agents of a broad spectrum of plant diseases ofeconomic importance, affecting ornamental, turf, vegetable, field,cereal and fruit crops. In the context of this disclosure, “protecting aplant from disease” or “control of a plant disease” includespreventative action (interruption of the fungal cycle of infection,colonization, symptom development and spore production) and/or curativeaction (inhibition of colonization of plant host tissues).

As used herein, the term “mode of action” (MOA) is as define by theFungicide Resistance Action Committee (FRAC), and is used to distinguishfungicides according to their biochemical mode of action in thebiosynthetic pathways of plant pathogens. FRAC-defined modes of actionsinclude (A) nucleic acid synthesis, (B) mitosis and cell division, (C)respiration, (D) amino acid and protein synthesis, (E) signaltransduction, (F) lipid synthesis and membrane integrity, (G) sterolbiosynthesis in membranes, (H) cell wall biosynthesis, (I) melaninsynthesis in cell wall, (P) host plant defense induction, (U) unknownmode of action, (NC) not classified and (M) multi-site contact activity.Each mode of action (i.e. letters A through M) contain one or moresubgroups (e.g., A includes subgroups A1, A2, A3 and A4) based either onindividual validated target sites of action, or in cases where theprecise target site is unknown, based on cross resistance profileswithin a group or in relation to other groups. Each of these subgroups(e.g., A1, A2, A3 and A4) is assigned a FRAC code (a number and/orletter). For example, the FRAC code for subgroup A1 is 4. Additionalinformation on target sites and FRAC codes can be obtained from publiclyavailable databases maintained, for example, by FRAC.

As used herein, the term “cross resistance” refers to the phenomenonthat occurs when a pathogen develops resistance to one fungicide andsimultaneously becomes resistant to one or more other fungicides. Theseother fungicides are typically, but not always, in the same chemicalclass or have the same target site of action, or can be detoxified bythe same mechanism.

Generally when a molecular fragment (i.e. radical) is denoted by aseries of atom symbols (e.g., C, H, N, O and S) the implicit point orpoints of attachment will be easily recognized by those skilled in theart. In some instances herein, particularly when alternative points ofattachment are possible, the point or points of attachment may beexplicitly indicated by a hyphen (“-”). For example, “—SCN” indicatesthat the point of attachment is the sulfur atom (i.e. thiocyanato, notisothiocyanato).

As used herein, the term “alkylating agent” refers to a chemicalcompound in which a carbon-containing radical is bound through a carbonatom to a leaving group such as halide or sulfonate, which isdisplaceable by bonding of a nucleophile to said carbon atom. Unlessotherwise indicated, the term “alkylating” does not limit thecarbon-containing radical to alkyl; the carbon-containing radicals inalkylating agents include the variety of carbon-bound substituentradicals specified, for example, for R².

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain and branched alkyl, such as, methyl, ethyl, n-propyl,i-propyl, and the different butyl, pentyl and hexyl isomers. “Alkenyl”includes straight-chain and branched alkenes such as ethenyl,1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenylisomers. “Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-hexadienyl. “Alkynyl” includes straight-chain and branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” also includes moieties comprisedof multiple triple bonds such as 2,5-hexadiynyl.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy,i-propyloxy, and the different butoxy isomers. “Alkenyloxy” includesstraight-chain and branched alkenyl attached to and linked through anoxygen atom. Examples of “alkenyloxy” include H₂C═CHCH₂O andCH₃CH═CHCH₂O. “Alkynyloxy” includes straight-chain and branchedalkynyloxy moieties. Examples of “alkynyloxy” include HC—CCH₂O andCH₃C—CCH₂O.

The term “alkylthio” includes straight-chain and branched alkylthiomoieties such as methylthio, ethylthio, and the different propylthio andbutylthio isomers. “Alkylsulfinyl” includes both enantiomers of analkylsulfinyl group. Examples of “alkylsulfinyl” include CH₃S(═O),CH₃CH₂S(═O), CH₃CH₂CH₂S(═O), (CH₃)₂CHS(═O), and the differentbutylsulfinyl isomers. Examples of “alkylsulfonyl” include CH₃S(═O)₂,CH₃CH₂S(═O)₂, CH₃CH₂CH₂S(═O)₂, (CH₃)₂CHS(═O)₂, and the differentbutylsulfonyl isomers.

“Alkylamino” includes an NH radical substituted with a straight-chain orbranched alkyl group. Examples of “alkylamino” include CH₃CH₂NH,CH₃CH₂CH₂NH, and (CH₃)₂CHCH₂NH. Examples of “dialkylamino” include(CH₃)₂N, (CH₃CH₂CH₂)₂N and CH₃CH₂(CH₃)N.

“Alkylcarbonyl” denotes a straight-chain or branched alkyl group bondedto a C(═O) moiety. Examples of “alkylcarbonyl” include CH₃C(═O),CH₃CH₂CH₂C(═O) and (CH₃)₂CHC(═O). Examples of “alkoxycarbonyl” includeCH₃OC(═O), CH₃CH₂OC(═O), CH₃CH₂CH₂OC(═O), (CH₃)₂CHOC(═O), and thedifferent butoxy-, pentoxy- and hexyloxycarbonyl isomers. Examples of“alkylaminocarbonyl” include CH₃NHC(═O), CH₃CH₂NHC(═O),CH₃CH₂CH₂NHC(═O), (CH₃)₂CHNHC(═O), and the different butylamino-,pentylamino- and hexylaminocarbonyl isomers. Examples of“dialkylaminocarbonyl” include (CH₃)₂NC(═O), (CH₃CH₂)₂NC(═O),CH₃CH₂(CH₃)NC(═O), (CH₃)₂CH(CH₃)NC(═O) and CH₃CH₂CH₂(CH₃)NC(═O).

“Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of“alkoxyalkyl” include CH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂OCH₂ andCH₃CH₂OCH₂CH₂. “Alkylthioalkyl” denotes alkylthio substitution on alkyl.Examples of “alkylthioalkyl” include CH₃SCH₂, CH₃SCH₂CH₂, CH₃CH₂SCH₂,CH₃CH₂CH₂SCH₂ and CH₃CH₂SCH₂CH₂; “alkylsulfinylalkyl” and“alkylsulfonylalkyl” include the corresponding sulfoxides and sulfones,respectively.

“Alkylcarbonylthio” denotes a straight-chain or branched alkylcarbonylattached to and linked through a sulfur atom. Examples of“alkylcarbonylthio” include CH₃C(═O)S, CH₃CH₂CH₂C(═O)S and(CH₃)₂CHC(═O)S. The term “alkylcarbonyloxy” denotes a straight-chain orbranched alkyl bonded to a C(═O)O moiety. Examples of “alkylcarbonyloxy”include CH₃CH₂C(═O)O and (CH₃)₂CHC(═O)O.

The term “alkylaminocarbonylalkyl” denotes a straight-chain or branchedalkylaminocarbonyl attached to alkyl. Examples of“alkylaminocarbonylalkyl” include (CH₃)₂CHCH₂NHC(═O)CH₂ andCH₃CH₂NHC(═O)CH₂. Examples of “dialkylaminocarbonylalkyl” includeCH₃CH₂CH₂(CH₃)NC(═O)CH₂ and (CH₃)₂NC(═O)CH₂.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyland cyclohexyl. The term “cycloalkylalkyl” denotes cycloalkylsubstitution on an alkyl moiety. Examples of “cycloalkylalkyl” includecyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moietiesbonded to a straight-chain or branched alkyl group.

“Cycloalkylamino” denotes an NH radical substituted with cycloalkyl.Examples of “cycloalkylamino” include cyclopropylamino andcyclohexylamino.

The term “halogen”, either alone or in compound words such as“haloalkyl”, or when used in descriptions such as “alkyl substitutedwith halogen” includes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl”, or when used indescriptions such as “alkyl substituted with halogen” said alkyl may bepartially or fully substituted with halogen atoms which may be the sameor different. Examples of “haloalkyl” or “alkyl substituted withhalogen” include F₃C, ClCH₂, CF₃CH₂ and CF₃CCl₂.

The terms “haloalkenyl”, “haloalkynyl” “haloalkoxy”, “haloalkylthio”,“haloalkylsulfinyl”, “haloalkylsulfonyl”, “halocycloalkyl”, and thelike, are defined analogously to the term “haloalkyl”. Examples of“haloalkenyl” include Cl₂C═CHCH₂ and CF₃CH₂CH═CH. Examples of“haloalkynyl” include HC≡CCHCl, CF₃C≡C, CCl₃C≡C and FCH₂C—CCH₂. Examplesof “haloalkoxy” include CF₃O, CCl₃CH₂O, F₂CHCH₂CH₂O and CF₃CH₂O.Examples of “haloalkylthio” include CCl₃S, CF₃S, CCl₃CH₂S andClCH₂CH₂CH₂S. Examples of “haloalkylsulfinyl” include CF₃S(═O),CCl₃S(═O), CF₃CH₂S(═O) and CF₃CF₂S(═O). Examples of “haloalkylsulfonyl”include CF₃S(═O)₂, CCl₃S(═O)₂, CF₃CH₂S(═O)₂ and CF₃CF₂S(═O)₂. Examplesof “halocycloalkyl” include 2-chlorocyclopropyl, 2-fluorocyclobutyl,3-bromocyclopentyl and 4-chorocyclohexyl.

“Hydroxyalkyl” denotes an alkyl group substituted with one hydroxygroup. Examples of “hydroxyalkyl” include HOCH₂CH₂, CH₃CH₂(OH)CH andHOCH₂CH₂CH₂CH₂.

“Trialkylsilyl” includes 3 branched and/or straight-chain alkyl radicalsattached to and linked through a silicon atom, such as trimethylsilyl,triethylsilyl and tert-butyldimethylsilyl.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 8. Forexample, C₁-C₄ alkylsulfonyl designates methylsulfonyl throughbutylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂; C₃ alkoxyalkyldesignates, for example, CH₃CH(OCH₃), CH₃OCH₂CH₂ or CH₃CH₂OCH₂; and C₄alkoxyalkyl designates the various isomers of an alkyl group substitutedwith an alkoxy group containing a total of four carbon atoms, examplesincluding CH₃CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.

The term “unsubstituted” in connection with a group such as a ring orring system means the group does not have any substituents other thanits one or more attachments to the remainder of Formula 1. The term“optionally substituted” means that the number of substituents can bezero. Unless otherwise indicated, optionally substituted groups may besubstituted with as many optional substituents as can be accommodated byreplacing a hydrogen atom with a non-hydrogen substituent on anyavailable carbon or nitrogen atom. Commonly, the number of optionalsubstituents (when present) ranges from 1 to 3. As used herein, the term“optionally substituted” is used interchangeably with the phrase“substituted or unsubstituted” or with the term “(un)substituted.” Thenumber of optional substituents may be restricted by an expressedlimitation. For example, the phrase “optionally substituted with up to 3substituents independently selected from R^(3a)” means that 0, 1, 2 or 3substituents can be present (if the number of potential connectionpoints allows). Similarly, the phrase “optionally substituted with up to5 substituents independently selected from R^(3a)” means that 0, 1, 2,3, 4 or 5 substituents can be present if the number of availableconnection points allows. When a range specified for the number ofsubstituents (e.g., k being an integer from 1 to 2 in Exhibit A) exceedsthe number of positions available for substituents on a ring (e.g., 1position available for (R³)_(k) on U-17 in Exhibit A), the actual higherend of the range is recognized to be the number of available positions.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can vary (e.g., (R³)_(k)in Exhibit A wherein k is 1 to 2), then said substituents areindependently selected from the group of defined substituents, unlessotherwise indicated. When a variable group is shown to be optionallyattached to a position, for example (R³)_(k) in Exhibit A wherein k maybe 0, then hydrogen may be at the position even if not recited in thedefinition of the variable group.

Naming of substituents in the present disclosure uses recognizedterminology providing conciseness in precisely conveying to thoseskilled in the art the chemical structure. For sake of conciseness,locant descriptors may be omitted.

Unless otherwise indicated, a “ring” or “ring system” as a component ofFormula 1 (e.g., substituent R¹) is carbocyclic or heterocyclic. Theterm “ring system” denotes two or more connected rings. The term“bicyclic ring system” denotes a ring system consisting of two ringssharing two or more common atoms. In a “fused bicyclic ring system” thecommon atoms are adjacent, and therefore the rings share two adjacentatoms and bond connecting them.

A ring can be part of an extended ring system containing more than tworings wherein substituents on the ring, are taken together to form theadditional rings, which may be in bicyclic a relationship with otherrings in the extended ring system.

The term “ring member” refers to an atom (e.g., C, O, N or S) or othermoiety (e.g., C(═O), C(═S) or S(═O)_(u)(═NR¹²)_(v)) forming the backboneof a ring or ring system. The term “aromatic” indicates that each ringatom is essentially in the same plane and has a p-orbital perpendicularto the ring plane, and that (4n+2) π electrons, where n is a positiveinteger, are associated with the ring to comply with Hückel's rule.

The term “carbocyclic ring” denotes a ring wherein the atoms forming thering backbone are selected only from carbon. Unless otherwise indicated,a carbocyclic ring can be a saturated, partially unsaturated, or fullyunsaturated ring. When a fully unsaturated carbocyclic ring satisfiesHückel's rule, then said ring is also called an “aromatic ring”.“Saturated carbocyclic” refers to a ring having a backbone consisting ofcarbon atoms linked to one another by single bonds; unless otherwisespecified, the remaining carbon valences are occupied by hydrogen atoms.

As used herein, the term “partially unsaturated ring” or “partiallyunsaturated heterocycle” refers to a ring which contains unsaturatedring atoms and one or more double bonds but which is not aromatic.

The terms “heterocyclic ring” or “heterocycle” denotes a ring wherein atleast one of the atoms forming the ring backbone is other than carbon.Unless otherwise indicated, a heterocyclic ring can be a saturated,partially unsaturated, or fully unsaturated ring. When a fullyunsaturated heterocyclic ring satisfies Hückel's rule, then said ring isalso called a “heteroaromatic ring” or “aromatic heterocyclic ring”.“Saturated heterocyclic ring” refers to a heterocyclic ring containingonly single bonds between ring members.

Unless otherwise indicated, heterocyclic rings and ring systems areattached to the remainder of Formula 1 through any available carbon ornitrogen atom by replacement of a hydrogen on said carbon or nitrogenatom.

Compounds of this invention can exist as one or more stereoisomers.Stereoisomers are isomers of identical constitution but differing in thearrangement of their atoms in space and include enantiomers,diastereomers, cis- and trans-isomers (also known as geometric isomers)and atropisomers. Atropisomers result from restricted rotation aboutsingle bonds where the rotational barrier is high enough to permitisolation of the isomeric species. One skilled in the art willappreciate that one stereoisomer may be more active and/or may exhibitbeneficial effects when enriched relative to the other stereoisomer(s)or when separated from the other stereoisomer(s). Additionally, theskilled artisan knows how to separate, enrich, and/or to selectivelyprepare said stereoisomers. For a comprehensive discussion of allaspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen,Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

Compounds of Formula 1 may be present as a mixture of stereoisomers,individual stereoisomers, or as an optically active form. For example,when Z² is —OC(R^(6a)R^(6b))—, wherein R^(6a) and R^(6b) are selectedfrom R⁶ and are different, then Formula 1 possesses a chiral center atthe carbon atom to which the R^(6a) and R^(6b) substituents are bonded.The two enantiomers are depicted as Formula 1′ and Formula 1″ below andthe chiral center is identified with an asterisk (*).

Compounds of Formula 1 comprise racemic mixtures, for example, equalamounts of the enantiomers of Formulae 1′ and 1″. In addition, compoundsof Formula 1 include compounds that are enriched compared to the racemicmixture in an enantiomer of Formula 1. Also included are the essentiallypure enantiomers of compounds of Formula 1, for example, Formula 1′ andFormula 1″.

Compounds of this invention can exist as one or more conformationalisomers due to restricted rotation about an amide bond (e.g., C(═O)—N)in Formula 1. This invention comprises mixtures of conformationalisomers. In addition, this invention includes compounds that areenriched in one conformer relative to others.

This invention comprises all stereoisomers, conformational isomers andmixtures thereof in all proportions as well as isotopic forms such asdeuterated compounds.

One skilled in the art will appreciate that not all nitrogen containingheterocycles can form N-oxides since the nitrogen requires an availablelone pair for oxidation to the oxide; one skilled in the art willrecognize those nitrogen-containing heterocycles which can formN-oxides. One skilled in the art will also recognize that tertiaryamines can form N-oxides.

Synthetic methods for the preparation of N-oxides of heterocycles andtertiary amines are very well known by one skilled in the art includingthe oxidation of heterocycles and tertiary amines with peroxy acids suchas peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide,alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate,and dioxiranes such as dimethyldioxirane. These methods for thepreparation of N-oxides have been extensively described and reviewed inthe literature, see for example: T. L. Gilchrist in ComprehensiveOrganic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press;M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol.3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R.Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol.43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B.Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A.R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H.Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry,vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., AcademicPress.

One skilled in the art recognizes that because in the environment andunder physiological conditions salts of chemical compounds are inequilibrium with their corresponding nonsalt forms, salts share thebiological utility of the nonsalt forms. Thus a wide variety of salts ofthe compounds of Formula 1 are useful for control of plant diseasescaused by fungal plant pathogens (i.e. are agriculturally suitable). Thesalts of the compounds of Formula 1 include acid-addition salts withinorganic or organic acids such as hydrobromic, hydrochloric, nitric,phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic,oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valericacids. When a compound of Formula 1 contains an acidic moiety such as acarboxylic acid, salts also include those formed with organic orinorganic bases such as pyridine, triethylamine or ammonia, or amides,hydrides, hydroxides or carbonates of sodium, potassium, lithium,calcium, magnesium or barium. Accordingly, the present inventioncomprises compounds selected from Formula 1, N-oxides and agriculturallysuitable salts, solvates and hydrates thereof.

Compounds selected from Formula 1, stereoisomers, tautomers, N-oxides,and salts thereof, typically exist in more than one form, and Formula 1thus includes all crystalline and non-crystalline forms of the compoundsthat Formula 1 represents. Non-crystalline forms include embodimentswhich are solids such as waxes and gums as well as embodiments which areliquids such as solutions and melts. Crystalline forms includeembodiments which represent essentially a single crystal type andembodiments which represent a mixture of polymorphs (i.e. differentcrystalline types). The term “polymorph” refers to a particularcrystalline form of a chemical compound that can crystallize indifferent crystalline forms, these forms having different arrangementsand/or conformations of the molecules in the crystal lattice. Althoughpolymorphs can have the same chemical composition, they can also differin composition due to the presence or absence of co-crystallized wateror other molecules, which can be weakly or strongly bound in thelattice.

Polymorphs can differ in such chemical, physical and biologicalproperties as crystal shape, density, hardness, color, chemicalstability, melting point, hygroscopicity, suspensibility, dissolutionrate and biological availability. One skilled in the art will appreciatethat a polymorph of a compound represented by Formula 1 can exhibitbeneficial effects (e.g., suitability for preparation of usefulformulations, improved biological performance) relative to anotherpolymorph or a mixture of polymorphs of the same compound represented byFormula 1. Preparation and isolation of a particular polymorph of acompound represented by Formula 1 can be achieved by methods known tothose skilled in the art including, for example, crystallization usingselected solvents and temperatures. For a comprehensive discussion ofpolymorphism see R. Hilfiker, Ed., Polymorphism in the PharmaceuticalIndustry, Wiley-VCH, Weinheim, 2006.

The compounds herein, and the agriculturally acceptable salts thereof,may exist in a continuum of solid states ranging from fully amorphous tofully crystalline. They may also exist in unsolvated and solvated forms.The term “solvate” describes a molecular complex comprising the compoundand one or more agriculturally acceptable solvent molecules (e.g.,EtOH). The term “hydrate” is a solvate in which the solvent is water.Agriculturally acceptable solvates include those in which the solventmay be isotopically substituted (e.g., D₂O, d₆-acetone, d₆-DMSO). Oneskilled in the art will understand that when in an aqueous media,compounds of Formula 1 may be present in a reversible equilibrium withcorresponding covalently hydrated forms at thetrifluoromethyl-oxadiazole ring as depicted by Formula 1.1 and Formula1.2 below.

A currently accepted classification system for solvates and hydrates oforganic compounds is one that distinguishes between isolated site,channel, and metal-ion coordinated solvates and hydrates. See, e.g., K.R. Morris (H. G. Brittain ed.) Polymorphism in Pharmaceutical Solids(1995). Isolated site solvates and hydrates are ones in which thesolvent (e.g., water) molecules are isolated from direct contact witheach other by intervening molecules of the organic compound. In channelsolvates, the solvent molecules lie in lattice channels where they arenext to other solvent molecules. In metal-ion coordinated solvates, thesolvent molecules are bonded to the metal ion.

Embodiments of the present invention as described in the Summary of theInvention include those described below. In the following Embodiments,Formula 1 includes stereoisomers, N-oxides, hydrates, and salts thereof,and reference to “a compound of Formula 1” includes the definitions ofsubstituents specified in the Summary of the Invention unless furtherdefined in the Embodiments.

Embodiment 1

A compound of Formula 1 wherein when R¹ is separate (i.e. not takentogether with R^(4a) or R^(4b) to form a ring), then R¹ is H; or C₁-C₆alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkylcarbonyl or C₂-C₆alkoxycarbonyl, each optionally substituted with up to 2 substituentsindependently selected from R²; or phenyl optionally substituted with upto 3 substituents independently selected from R^(3a); or a 3- to7-membered nonaromatic carbocyclic ring, wherein up to 2 carbon atomring members are independently selected from C(═O) and C(═S), each ringoptionally substituted with up to 3 substituents independently selectedfrom R^(3a); or a 5- to 6-membered heterocyclic ring, each ringcontaining ring members selected from carbon atoms and 1 to 4heteroatoms independently selected from up to 2 O, up to 2 S and up to 4N atoms, wherein up to 2 carbon atom ring members are independentlyselected from C(═O) and C(═S), each ring optionally substituted with upto 3 substituents independently selected from R^(3a) on carbon atom ringmembers and R^(3b) on nitrogen atom ring members.

Embodiment 2

A compound of Embodiment 1 wherein R¹ is H; or C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkylcarbonyl or C₂-C₆ alkoxycarbonyl,each optionally substituted with up to 2 substituents independentlyselected from R²; or phenyl optionally substituted with up to 3substituents independently selected from R^(3a); or C₃-C₆ cycloalkyloptionally substituted with up to 2 substituents independently selectedfrom R^(3a); or a 5- to 6-membered heterocyclic ring, each ringcontaining ring members selected from carbon atoms and 1 to 4heteroatoms independently selected from up to 2 O, up to 2 S and up to 4N atoms, wherein up to 2 carbon atom ring members are independentlyselected from C(═O) and C(═S), each ring optionally substituted with upto 3 substituents independently selected from R^(3a) on carbon atom ringmembers and R^(3b) on nitrogen atom ring members.

Embodiment 3

A compound of Embodiment 2 wherein R¹ is H; or C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, each optionally substituted with up to 2substituents independently selected from R²; or phenyl optionallysubstituted with up to 3 substituents independently selected fromR^(3a); or C₃-C₆ cycloalkyl optionally substituted with up to 2substituents independently selected from R^(3a); or a 5- to 6-memberedheterocyclic ring, each ring containing ring members selected fromcarbon atoms and 1 to 4 heteroatoms independently selected from up to 2O, up to 2 S and up to 4 N atoms, wherein up to 2 carbon atom ringmembers are independently selected from C(═O) and C(═S), each ringoptionally substituted with up to 3 substituents independently selectedfrom R^(3a) on carbon atom ring members and R^(3b) on nitrogen atom ringmembers.

Embodiment 4

A compound of Embodiment 2 wherein R¹ is H; or C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkylcarbonyl or C₂-C₆ alkoxycarbonyl,each optionally substituted with up to 2 substituents independentlyselected from R²; or C₃-C₆ cycloalkyl optionally substituted with up to2 substituents independently selected from R^(3a).

Embodiment 5

A compound of Embodiment 4 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl or C₂-C₄ alkoxycarbonyl,each optionally substituted with up to 1 substituent selected from R²;or C₃-C₆ cycloalkyl optionally substituted with up to 2 substituentsindependently selected from R^(3a).

Embodiment 6

A compound of Embodiment 5 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl or C₂-C₄ alkoxycarbonyl,each optionally substituted with up to 1 substituent selected from R²;or cycloproply optionally substituted with up to 2 substituentsindependently selected from R^(3a).

Embodiment 7

A compound of Formula 1 or Embodiment 1 wherein when R¹ is separate(i.e. not taken together with R^(4a) or R^(4b) to form a ring), then R¹is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkylcarbonylor C₂-C₆ alkoxycarbonyl, each optionally substituted with up to 2substituents independently selected from R²; or R¹ is selected from U-1through U-79 as shown in Exhibit A

-   -   wherein when R³ is attached to a carbon ring member, said R³ is        selected from R^(3a), and when R³ is attached to a nitrogen ring        member (e.g., in U-4, U-11 through U-15, U-24 through U-26, U-31        or U-35), said R³ is selected from R^(3b); and k is 0, 1 or 2.

Embodiment 7a

A compound of Embodiment 7 wherein R¹ is selected from U-1 through U-79.

Embodiment 8

A compound of Embodiment 7 wherein R¹ is H; or C₁-C₆ alkyl, C₂-C₆alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkylcarbonyl or C₂-C₆ alkoxycarbonyl,each optionally substituted with up to 2 substituents independentlyselected from R²; or U-1 through U-53, U-55, U-58, U-62, U-66 or U-74through U-79.

Embodiment 8a

A compound of Embodiment 8 wherein R¹ is U-1 through U-53, U-55, U-58,U-62, U-66 or U-74 through U-79.

Embodiment 9

A compound of Embodiment 8 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl or C₂-C₄ alkoxycarbonyl,each optionally substituted with up to 2 substituents independentlyselected from R²; or U-1, U-2, U-3, U-5, U-20, U-21, U-28, U-36, U-37,U-38, U-39, U-41, U-43, U-50, U-53, U-55, U-58, U-62 or U-74 throughU-78.

Embodiment 9a

A compound of Embodiment 9 wherein R¹ is U-1, U-2, U-3, U-5, U-20, U-21,U-28, U-36, U-37, U-38, U-39, U-41, U-43, U-50, U-53, U-55, U-58, U-62or U-74 through U-78.

Embodiment 10

A compound of Embodiment 9 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl or C₂-C₄ alkoxycarbonyl,each optionally substituted with up to 1 substituent selected from R²;or U-36, U-37, U-38, U-39, U-41, U-50, U-53, U-55 or U-58.

Embodiment 10a

A compound of Embodiment 10 wherein R¹ is U-36, U-37, U-38, U-39, U-41,U-50, U-53, U-55 or U-58.

Embodiment 11

A compound of Embodiment 10 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl or C₂-C₄ alkoxycarbonyl,each optionally substituted with up to 1 substituent selected from R²;or U-36, U-37, U-39, U-50, U-53 or U-55.

Embodiment 11a

A compound of Embodiment 11 wherein R¹ is U-36, U-37, U-39, U-50, U-53or U-55.

Embodiment 12

A compound of Embodiment 11 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl or C₂-C₄ alkynyl, each optionally substituted with up to 1substituent selected from R²; or U-36, U-39, U-50, U-53 or U-55.

Embodiment 13

A compound of Embodiment 12 wherein R¹ is H, C₁-C₄ alkyl, C₂-C₄ alkenyl,C₂-C₄ alkynyl, U-36, U-39, U-50, U-53 or U-55.

Embodiment 14

A compound of Embodiment 11 wherein R¹ is H, C₁-C₄ alkyl, C₂-C₄ alkenyl,C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl, C₂-C₄ alkoxycarbonyl or U-50.

Embodiment 14a

A compound of Embodiment 14 wherein R¹ is H, C₁-C₄ alkyl, C₂-C₄ alkenyl,C₂-C₄ alkynyl or U-50.

Embodiment 15

A compound of Embodiments 14 or 14a wherein R¹ is U-50.

Embodiment 16

A compound of Formula 1 wherein when R¹ is separate (i.e. not takentogether with R^(4a) or R^(4b) to form a ring), then R¹ is H; or C₁-C₆alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆ alkylcarbonyl or C₂-C₆alkoxycarbonyl, each optionally substituted with up to 1 substituentselected from R²; or U-38, U-50 or U-53.

Embodiment 17

A compound of Embodiment 16 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl or C₂-C₄ alkoxycarbonyl,each optionally substituted with up to 1 substituent selected from R²;or U-38, U-50 or U-53.

Embodiment 18

A compound of Embodiment 17 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₂-C₄ alkylcarbonyl or C₂-C₄ alkoxycarbonyl,each optionally substituted with up to 1 substituent selected from R²;or U-50.

Embodiment 19

A compound of Embodiment 18 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl or C₂-C₄ alkynyl, each optionally substituted with up to 1substituent selected from R²; or U-50.

Embodiment 20

A compound of Embodiment 19 wherein R¹ is H; or C₁-C₄ alkyl, C₂-C₄alkenyl or C₂-C₄ alkynyl, each optionally substituted with up to 1substituent selected from R².

Embodiment 21

A compound of Embodiment 20 wherein R¹ is H, C₁-C₄ alkyl, C₂-C₄ alkenylor C₂-C₄ alkynyl.

Embodiment 22

A compound of Embodiment 21 wherein R¹ is H, C₁-C₂ alkyl, C₂-C₄ alkenylor C₂-C₄ alkynyl.

Embodiment 23

A compound of Embodiment 22 wherein R¹ is H, C₁-C₂ alkyl or C₂-C₄alkynyl.

Embodiment 24

A compound of Embodiment 23 wherein R¹ is H or C₁-C₂ alkyl.

Embodiment 25

A compound of Embodiment 24 wherein R¹ is H.

Embodiment 26

A compound of Formula 1 or any one of Embodiments 1 through 25 whereinZ¹ is —CH═NNR^(4b)—.

Embodiment 27

A compound of Formula 1 or any one of Embodiments 1 through 25 whereinZ¹ is O, —(CH₂)_(n)NR^(4a)— or —(CH₂)_(n)NR^(4a)NR^(4b)—.

Embodiment 27a

A compound of Formula 1 or any one of Embodiments 1 through 25 whereinZ¹ is O, —NR^(4a)— or —NR^(4a)NR^(4b)—.

Embodiment 28

A compound of Embodiment 27a wherein Z¹ is O or —NR^(4a)—.

Embodiment 29

A compound of Formula 1 or any one of Embodiments 1 through 25 whereinZ¹ is —(CH₂)_(n)NR^(4a)— or —(CH₂)_(n)NR^(4a)NR^(4b)—.

Embodiment 30

A compound of Embodiment 29 wherein Z¹ is —(CH₂)_(n)NR^(4a).

Embodiment 31

A compound of Embodiment 29 wherein Z¹ is —(CH₂)_(n)NR^(4a)NR^(4b).

Embodiment 32

A compound of Embodiment 29 wherein Z¹ is —NR^(4a)—.

Embodiment 33

A compound of Embodiment 29 wherein Z¹ is —NR^(4a)NR^(4b).

Embodiment 34

A compound of Formula 1 or any one of Embodiments 1 through 31 wherein nis 0.

Embodiment 35

A compound of Formula 1 or any one of Embodiments 1 through 34 wherein Wis O.

Embodiment 36

A compound of Formula 1 or any one of Embodiments 1 through 34 wherein Wis S.

Embodiment 37

A compound of Formula 1 or any one of Embodiments 1 through 36 whereinZ² is —O(CH₂)_(m)—, —OCH₂CH₂O— or —NR⁵N═CH—, each carbon atom optionallysubstituted with up to 1 substituent selected from R⁶.

Embodiment 38

A compound of Embodiment 37 wherein Z² is —O(CH₂)_(m)—.

Embodiment 39

A compound of Embodiment 37 wherein Z² is —OCH₂CH₂O—.

Embodiment 40

A compound of Embodiment 37 wherein Z² is —NR⁵N═CH—.

Embodiment 41

A compound of Formula 1 or any one of Embodiments 1 through 36 whereinZ² is —O(CH₂)_(m)— or —OCH₂CH₂O—, each carbon atom optionallysubstituted with up to 2 substituents independently selected from R⁶.

Embodiment 42

A compound of Embodiment 41 wherein Z² is —O(CH₂)_(m)—, each carbon atomoptionally substituted with up to 2 substituents independently selectedfrom R⁶.

Embodiment 43

A compound of Embodiment 42 wherein Z² is —O(CH₂)_(m)—, each carbon atomoptionally substituted with up to 1 substituent selected from R⁶.

Embodiment 44

A compound of Formula 1 or any one of Embodiments 1 through 36 whereinZ² is —O(CH₂)_(m)— or —NR⁵N═CH—, each carbon atom optionally substitutedwith up to 2 substituents independently selected from R⁶.

Embodiment 44a

A compound of Embodiment 44 wherein Z² is —O(CH₂)_(m)— or —NR⁵N═CH—,each carbon atom optionally substituted with up to 1 substituentselected from R⁶.

Embodiment 45

A compound of Embodiments 44 or 44a wherein Z² is —O(CH₂)_(m)— or—NR⁵N═CH—.

Embodiment 46

A compound of Formula 1 or any one of Embodiments 1 through 45 wherein mis 1 or 2.

Embodiment 47

A compound of Formula 1 or any one of Embodiments 1 through 45 wherein mis 3.

Embodiment 48

A compound of Embodiment 46 wherein m is 1.

Embodiment 49

A compound of Embodiment 46 wherein m is 2.

Embodiment 50

A compound of Formula 1 or any one of Embodiments 1 through 49 wherein Jis phenyl optionally substituted with up to 2 substituents independentlyselected from R⁷; or a 5- to 6-membered heteroaromatic ring, each ringcontaining ring members selected from carbon atoms and 1 to 4heteroatoms independently selected from up to 2 O, up to 2 S and up to 4N atoms, each ring optionally substituted with up to 2 substituentsindependently selected from R⁷ on carbon atom ring members and R⁸ onnitrogen atom ring members.

Embodiment 51

A compound of Formula 1 or Embodiment 50 wherein J is selected from J-1through J-71 as shown in Exhibit B

-   -   wherein the bond projecting to the left is bonded to Z², and the        bond projecting to the right is bonded to the oxadiazole ring in        Formula 1; each R^(7a) is independently H or R⁷; and R^(8b) is        H; provided that at most only two of R^(7a) are other than H.

Embodiment 51a

A compound of Embodiment 51 wherein each R^(7a) is H.

Embodiment 52

A compound of Embodiments 51 or 51a wherein J is J-1 through J-5, J-15,J-17, J-18, J-37 through J-41, J-45, J-50 through J-56 or J-60 throughJ-67.

Embodiment 53

A compound of Embodiment 52 wherein J is J-1, J-4, J-15, J-18, J-37,J-40, J-45, J-50, J-51, J-52, J-60, J-61, J-62, J-63 or J-64.

Embodiment 54

A compound of Embodiment 53 wherein J is J-4, J-18, J-40, J-50, J-51,J-52 or J-60.

Embodiment 55

A compound of Embodiment 54 wherein J is J-40, J-50, J-51 or J-52.

Embodiment 55a

A compound of Embodiment 55 wherein J is J-50, J-51 or J-52.

Embodiment 56

A compound of Embodiment 55 wherein J is J-40 or J-50.

Embodiment 57

A compound of Embodiment 56 wherein J is J-40.

Embodiment 58

A compound of Embodiment 56 wherein J is J-50.

Embodiment 59

A compound of Embodiment 55 wherein J is J-51.

Embodiment 60

A compound of Embodiment 55 wherein J is J-52.

Embodiment 61

A compound of Formula 1 or any one of Embodiments 1 through 60 whereineach R² is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl,C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy,C₂-C₄ alkylcarbonyl, C₂-C₄ haloalkylcarbonyl or C₂-C₅ alkoxycarbonyl; orphenyl, pyridinyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl,isoxazolyl, thienyl, furanyl, pyrrolidinyl, isoxazolinyl,tetrahydrofuranyl, piperidinyl, morpholinyl or piperazinyl, eachoptionally substituted with up to 3 substituents independently selectedfrom R^(3c) on carbon atom ring members and R^(3d) on nitrogen atom ringmembers.

Embodiment 62

A compound of Embodiment 61 wherein each R² is independently halogen,cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄ alkylcarbonyl,C₂-C₄ haloalkylcarbonyl or C₂-C₅ alkoxycarbonyl; or phenyl, pyridinyl,pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, isoxazolinyl,tetrahydrofuranyl, piperidinyl, morpholinyl or piperazinyl, eachoptionally substituted with up to 2 substituents independently selectedfrom R^(3c) on carbon atom ring members and R^(3d) on nitrogen atom ringmembers.

Embodiment 62a

A compound of Embodiment 62 wherein each R² is independently halogen,cyano, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkoxy; or phenyl, pyridinyl,pyrazolyl, imidazolyl, triazolyl, pyrrolidinyl, isoxazolinyl,tetrahydrofuranyl, piperidinyl, morpholinyl or piperazinyl, eachoptionally substituted with up to 2 substituents independently selectedfrom R^(3c) on carbon atom ring members and R^(3d) on nitrogen atom ringmembers.

Embodiment 63

A compound of Embodiment 62 wherein each R² is independently halogen,cyano, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkoxy; or phenyl, pyridinyl,imidazolyl, triazolyl, pyrrolidinyl, piperidinyl, morpholinyl orpiperazinyl, each optionally substituted with up to 2 substituentsindependently selected from R^(3c) on carbon atom ring members andR^(3d) on nitrogen atom ring members.

Embodiment 64

A compound of Embodiment 63 wherein each R² is independently halogen,cyano, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₃-C₆ halocycloalkyl or C₁-C₃alkoxy; or phenyl, pyridinyl, imidazolyl, triazolyl, pyrrolidinyl,piperidinyl, morpholinyl or piperazinyl, each optionally substitutedwith up to 1 substituent selected from R^(3c) on carbon atom ringmembers and R^(3d) on nitrogen atom ring members.

Embodiment 65

A compound of Formula 1 or any one of Embodiments 1 through 61 whereineach R² is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl,C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy,C₂-C₄ alkylcarbonyl, C₂-C₄ haloalkylcarbonyl or C₂-C₅ alkoxycarbonyl.

Embodiment 66

A compound of Embodiment 65 wherein each R² is independently halogen,cyano, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆halocycloalkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkoxy.

Embodiment 67

A compound of Embodiment 66 wherein each R² is independently halogen,C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkoxy.

Embodiment 68

A compound of Embodiment 67 wherein each R² is independently C₁-C₃alkyl.

Embodiment 69

A compound of Embodiment 66 wherein each R² is independently halogen,cyano, C₁-C₃ alkyl or C₁-C₃ alkoxy.

Embodiment 70

A compound of Formula 1 or any one of Embodiments 1 through 61 whereineach R² is independently phenyl, pyridinyl, pyrazolyl, imidazolyl,triazolyl, oxazolyl, isoxazolyl, thienyl, furanyl, pyrrolidinyl,isoxazolinyl, tetrahydrofuranyl, piperidinyl, morpholinyl orpiperazinyl, each optionally substituted with up to 3 substituentsindependently selected from R^(3c) on carbon atom ring members andR^(3d) on nitrogen atom ring members.

Embodiment 71

A compound of Embodiment 70 wherein each R² is independently phenyl,pyridinyl, imidazolyl, triazolyl, pyrrolidinyl, piperidinyl, morpholinylor piperazinyl, each optionally substituted with up to 2 substituentsindependently selected from R^(3c) on carbon atom ring members andR^(3d) on nitrogen atom ring members.

Embodiment 72

A compound of Embodiment 71 wherein each R² is phenyl optionallysubstituted with up to 2 substituents independently selected from R^(3c)Embodiment 73. A compound of Formula 1 or any one of Embodiments 1through 72 wherein each R^(3a) and R^(3c) when taken alone (i.e. nottaken together with R^(4a) or R^(4b)) is independently halogen, cyano,nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₆cycloalkyl, C₄-C₇ cycloalkylalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄alkenyloxy, C₂-C₄ alkynyloxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio,C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylsulfinyl, C₁-C₄ alkylsulfonyl, C₁-C₄haloalkylsulfonyl, C₁-C₄ alkylsulfonyloxy, C₁-C₄ alkylamino, C₂-C₈dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₄ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl or C₃-C₈ dialkylaminocarbonyl.

Embodiment 74

A compound of Embodiment 73 wherein each R^(3a) and R^(3c) isindependently halogen, cyano, nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₃-C₆ cycloalkyl, C₁-C₄ alkoxy, C₁-C₄haloalkoxy, C₂-C₄ alkenyloxy, C₂-C₄ alkynyloxy, C₁-C₄ alkylthio, C₁-C₄haloalkylthio, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄alkylsulfonyloxy, C₁-C₄ alkylamino, C₂-C₈ dialkylamino, C₃-C₆cycloalkylamino, C₂-C₄ alkylcarbonyl, C₂-C₅ alkoxycarbonyl, C₂-C₅alkylaminocarbonyl or C₃-C₇ dialkylaminocarbonyl.

Embodiment 75

A compound of Embodiment 74 wherein each R^(3a) and R^(3c) isindependently halogen, cyano, nitro, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₃alkenyl, C₂-C₃ alkynyl, C₃-C₆ cycloalkyl, C₁-C₃ alkoxy, C₁-C₃haloalkoxy, C₂-C₃ alkenyloxy, C₂-C₃ alkynyloxy, C₁-C₄ alkylsulfonyl,C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylsulfonyloxy, C₂-C₄ alkylcarbonyl,C₂-C₅ alkoxycarbonyl, C₂-C₅ alkylaminocarbonyl or C₃-C₇dialkylaminocarbonyl.

Embodiment 76

A compound of Embodiment 75 wherein each R^(3a) and R^(3c) isindependently halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy orC₁-C₃ haloalkoxy.

Embodiment 77

A compound of Embodiment 76 wherein each R^(3a) and R^(3c) isindependently halogen, methyl, ethyl, methoxy or C₁-C₂ haloalkoxy.

Embodiment 77a

A compound of Embodiment 77 wherein each R^(3a) and R^(3c) isindependently halogen, methyl or methoxy.

Embodiment 78

A compound of Embodiment 75 wherein each R^(3a) and R^(3c) isindependently halogen, cyano, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₂-C₃alkenyl, C₂-C₃ alkynyl, C₁-C₂ alkoxy, C₂-C₃ alkenyloxy, C₂-C₃alkynyloxy, C₂-C₄ alkylcarbonyl, C₂-C₅ alkoxycarbonyl, C₂-C₅alkylaminocarbonyl or C₃-C₇ dialkylaminocarbonyl.

Embodiment 79

A compound of Embodiment 78 wherein each R^(3a) and R^(3c) isindependently halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₂-C₃ alkenyl,C₂-C₃ alkynyl, C₁-C₂ alkoxy, C₂-C₃ alkenyloxy, C₂-C₃ alkynyloxy, C₂-C₄alkylcarbonyl or C₂-C₅ alkoxycarbonyl.

Embodiment 80

A compound of Embodiment 79 wherein each R^(3a) and R^(3c) isindependently halogen, C₁-C₂ alkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, C₂-C₃alkenyloxy, C₂-C₃ alkynyloxy, C₂-C₄ alkylcarbonyl or C₂-C₅alkoxycarbonyl.

Embodiment 81

A compound of Embodiment 79 wherein each R^(3a) and R^(3c) isindependently halogen, C₁-C₂ alkyl, C₂-C₄ alkylcarbonyl or C₂-C₅alkoxycarbonyl.

Embodiment 81a

A compound of Embodiment 81 wherein each R^(3a) and R^(3c) isindependently C₂-C₄ alkylcarbonyl or C₂-C₄ alkoxycarbonyl.

Embodiment 81b

A compound of Embodiment 81 wherein each R^(3a) and R^(3c) isindependently Br, Cl, F, methyl, C₂-C₄ alkylcarbonyl or C₂-C₄alkoxycarbonyl.

Embodiment 82

A compound of Formula 1 or any one of Embodiments 1 through 81b whereineach R^(3b) and R^(3d) when taken alone (i.e. not taken together withR^(4a) or R^(4b)) is independently C₁-C₂ alkyl, C₁-C₂ alkoxy, C₂-C₃alkylcarbonyl or C₂-C₃ alkoxycarbonyl.

Embodiment 83

A compound of Embodiment 82 wherein each R^(3b) and R^(3d) isindependently methyl, methylcarbonyl or methoxycarbonyl.

Embodiment 84

A compound of Embodiment 83 wherein each R^(3b) and R^(3d) is methyl.

Embodiment 85

A compound of Formula 1 or any one of Embodiments 1 through 84 whereinR^(4a) and R^(4b) when taken alone (i.e. not taken together with R¹,R^(3a) or R^(3b)) are each independently H, hydroxy, C₁-C₄ alkyl, C₁-C₄haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy,C₂-C₄ alkoxyalkyl, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, C₂-C₄alkylcarbonyl, C₂-C₄ haloalkylcarbonyl, C₂-C₅ alkoxycarbonyl, C₂-C₅alkylaminocarbonyl or C₃-C₅ dialkylaminocarbonyl.

Embodiment 86

A compound of Embodiment 85 wherein R^(4a) and R^(4b) are eachindependently H, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₃ alkenyl, C₂-C₃alkynyl, C₂-C₃ alkoxyalkyl, C₁-C₃ alkylsulfonyl, C₁-C₃haloalkylsulfonyl, C₂-C₃ alkylcarbonyl, C₂-C₃ haloalkylcarbonyl, C₂-C₃alkoxycarbonyl, C₂-C₃ alkylaminocarbonyl or C₃-C₅ dialkylaminocarbonyl.

Embodiment 87

A compound of Embodiment 86 wherein R^(4a) and R^(4b) are eachindependently H, methyl, C₁-C₂ haloalkyl, methoxymethyl, methylsulfonyl,methylcarbonyl or methoxycarbonyl.

Embodiment 88

A compound of Embodiment 86 wherein R^(4a) and R^(4b) are eachindependently H, methyl or ethyl.

Embodiment 89

A compound of Embodiment 88 wherein R^(4a) and R^(4b) are eachindependently H or methyl.

Embodiment 89a

A compound of Embodiment 89 wherein R^(4a) and R^(4b) are each H.

Embodiment 90

A compound of Formula 1 or any one of Embodiments 1 through 89a whereinwhen one pair of R¹ and R^(4a) substituents or one pair of R¹ and R^(4b)substituents are taken together with the atoms to which they areattached to form a ring, said ring is a 5- to 7-membered ring containingring members selected from carbon atoms and optionally up to 3heteroatoms independently selected from up to 1 O, up to 1 S and up to 2N atoms, each ring optionally substituted with up to 3 substituentsindependently selected from R⁹.

Embodiment 91

A compound of Embodiment 90 wherein one pair of R¹ and R^(4a)substituents or one pair of R¹ and R^(4b) substituents are takentogether with the atoms to which they are attached to form a 5- to6-membered ring containing ring members selected from carbon atoms andoptionally up to 3 heteroatoms independently selected from up to 1 O, upto 1 S and up to 2 N atoms, each ring optionally substituted with up to3 substituents independently selected from R⁹.

Embodiment 92

A compound of Embodiment 91 wherein one pair of R¹ and R^(4a)substituents or one pair of R¹ and R^(4b) substituents are takentogether with the atoms to which they are attached to form a 5- to6-membered ring containing ring members selected from carbon atoms andoptionally up to 3 heteroatoms independently selected from up to 1 O, upto 1 S and up to 2 N atoms, each ring optionally substituted with up to2 substituents independently selected from R⁹.

Embodiment 92a

A compound of Embodiment 92 wherein one pair of R¹ and R^(4a)substituents or one pair of R¹ and R^(4b) substituents are takentogether with the atoms to which they are attached to form a pyrazolyl,imidazolyl, pyrrolidinyl, isoxazolinyl, piperidinyl, morpholinyl orpiperazinyl ring, each ring optionally substituted with up to 2substituents independently selected from R⁹.

Embodiment 92b

A compound of Embodiment 92a wherein one pair of R¹ and R^(4a)substituents are taken together with the atoms to which they areattached to form a pyrazolyl, imidazolyl, pyrrolidinyl, isoxazolinyl,piperidinyl, morpholinyl or piperazinyl ring, each ring optionallysubstituted with up to 2 substituents independently selected from R⁹.

Embodiment 92c

A compound of Embodiment 92b wherein one pair of R¹ and R^(4a)substituents are taken together with the atoms to which they areattached to form a pyrazolyl or imidazolyl ring, each ring optionallysubstituted with up to 2 substituents independently selected from R⁹.

Embodiment 92d

A compound of Embodiment 92c wherein one pair of R¹ and R^(4a)substituents are taken together with the atoms to which they areattached to form an imidazolyl ring, the ring optionally substitutedwith up to 2 substituents independently selected from R⁹.

Embodiment 93

A compound of Formula 1 or any one of Embodiments 1 through 92d whereinwhen one pair of R^(3a) and R^(4a) substituents or one pair of R^(3a)and R^(4b) substituents are taken together with the atoms to which theyare attached to form a ring, said ring is a 5- to 7-membered ringcontaining ring members selected from carbon atoms and optionally up to3 heteroatoms independently selected from up to 1 O, up to 1 S and up to2 N atoms, each ring optionally substituted with up to 3 substituentsindependently selected from R¹⁰.

Embodiment 94

A compound of Embodiment 93 wherein one pair of R^(3a) and R^(4a)substituents or one pair of R^(3a) and R^(4b) substituents are takentogether with the atoms to which they are attached to form a 5- to6-membered ring containing ring members selected from carbon atoms andoptionally up to 3 heteroatoms independently selected from up to 1 O, upto 1 S and up to 2 N atoms, each ring optionally substituted with up to3 substituents independently selected from R¹⁰.

Embodiment 95

A compound of Embodiment 94 wherein one pair of R^(3a) and R^(4a)substituents or one pair of R^(3a) and R^(4b) substituents are takentogether with the atoms to which they are attached to form a 5- to6-membered ring containing ring members selected from carbon atoms andoptionally up to 3 heteroatoms independently selected from up to 1 O, upto 1 S and up to 2 N atoms, each ring optionally substituted with up to2 substituents independently selected from R¹⁰.

Embodiment 96

A compound of Formula 1 or any one of Embodiments 1 through 95 whereinwhen one pair of R^(3b) and R^(4a) substituents or one pair of R^(3b)and R^(4b) substituents are taken together with the nitrogen atoms towhich they are attached to form a ring, said ring is a 5- to 7-memberedring containing ring members selected from carbon atoms and optionallyup to 3 heteroatoms independently selected from up to 1 O, up to 1 S andup to 2 N atoms, each ring optionally substituted with up to 3substituents independently selected from R¹¹.

Embodiment 97

A compound of Embodiment 96 wherein one pair of R^(3b) and R^(4a)substituents or one pair of R^(3b) and R^(4b) substituents are takentogether with the nitrogen atoms to which they are attached to form a 5-to 6-membered ring containing ring members selected from carbon atomsand optionally up to 3 heteroatoms independently selected from up to 1O, up to 1 S and up to 2 N atoms, each ring optionally substituted withup to 3 substituents independently selected from R¹¹.

Embodiment 98

A compound of Embodiment 97 wherein one pair of R^(3b) and R^(4a)substituents or one pair of R^(3b) and R^(4b) substituents are takentogether with the nitrogen atoms to which they are attached to form a 5-to 6-membered ring containing ring members selected from carbon atomsand optionally up to 3 heteroatoms independently selected from up to 1O, up to 1 S and up to 2 N atoms, each ring optionally substituted withup to 2 substituents independently selected from R¹¹.

Embodiment 99

A compound of Formula 1 or any one of Embodiments 1 through 98 whereinR⁵ is H, hydroxy, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl,C₂-C₄ alkynyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄ alkoxyalkyl, C₁-C₄alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, C₂-C₄ alkylcarbonyl, C₂-C₄haloalkylcarbonyl, C₂-C₅ alkoxycarbonyl, C₃-C₅ alkoxycarbonylalkyl,C₂-C₅ alkylaminocarbonyl or C₃-C₅ dialkylaminocarbonyl.

Embodiment 100

A compound of Embodiment 99 wherein R⁵ is H, hydroxy, cyano, C₁-C₄alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄ alkoxy,C₁-C₄ haloalkoxy, C₂-C₄ alkoxyalkyl, C₁-C₄ alkylsulfonyl, C₁-C₄haloalkylsulfonyl, C₂-C₄ alkylcarbonyl, C₂-C₄ haloalkylcarbonyl, C₂-C₅alkoxycarbonyl, C₂-C₅ alkylaminocarbonyl or C₃-C₅ dialkylaminocarbonyl.

Embodiment 101

A compound of Embodiment 100 wherein R⁵ is H, C₁-C₃ alkyl, C₁-C₃haloalkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, C₂-C₃ alkoxyalkyl, C₁-C₃alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₂-C₃ alkylcarbonyl, C₂-C₃haloalkylcarbonyl, C₂-C₃ alkoxycarbonyl, C₂-C₅ alkylaminocarbonyl orC₃-C₅ dialkylaminocarbonyl.

Embodiment 102

A compound of Embodiment 101 wherein R⁵ is H, methyl, methoxymethyl,methylcarbonyl or methoxycarbonyl.

Embodiment 103

A compound of Embodiment 102 wherein R⁵ is H or methyl.

Embodiment 104

A compound of Embodiment 103 wherein R⁵ is H.

Embodiment 105

A compound of Formula 1 or any one of Embodiments 1 through 104 whereineach R⁶ is independently halogen, cyano, nitro, C₁-C₂ alkyl, C₁-C₂haloalkyl, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy.

Embodiment 106

A compound of Embodiment 105 wherein each R⁶ is independently halogen,cyano, nitro, methyl, trifluoromethyl or methoxy.

Embodiment 107

A compound of Embodiment 106 wherein each R⁶ is methyl or methoxy.

Embodiment 108

A compound of Formula 1 or any one of Embodiments 1 through 104 whereineach R⁶ is independently halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂alkoxy or C₂-C₄ alkoxyalkyl; or phenyl optionally substituted with up to2 substituents independently selected from R¹³.

Embodiment 109

A compound of Embodiment 108 wherein each R⁶ is independently methyl,methoxy or C₂-C₄ alkoxyalkyl; or phenyl optionally substituted with upto 2 substituents independently selected from R¹³.

Embodiment 110

A compound of Embodiment 109 wherein each R⁶ is independently methyl orCH₃OCH₂; or phenyl optionally substituted with up to 1 substituentselected from R¹³.

Embodiment 111

A compound of Embodiment 110 wherein each R⁶ is independently methyl; orphenyl optionally substituted with up to 2 substituents independentlyselected from R¹³.

Embodiment 112

A compound of Embodiment 111 wherein each R⁶ is independently methyl; orphenyl optionally substituted with up to 1 substituent selected fromR¹³.

Embodiment 113

A compound of Embodiment 112 wherein each R⁶ is independently methyl orphenyl.

Embodiment 114

A compound of Embodiment 113 wherein each R⁶ is methyl.

Embodiment 115

A compound of Formula 1 or any one of Embodiments 1 through 114 whereineach R⁷ is independently halogen, hydroxy, cyano, amino, nitro, C₁-C₄alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄hydroxyalkyl, C₃-C₆ cycloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄alkenyloxy, C₂-C₄ alkynyloxy, C₂-C₄ alkoxyalkyl, C₁-C₄ alkylthio, C₁-C₄haloalkylthio, C₁-C₄ alkylsulfinyl, C₁-C₄ haloalkylsulfinyl, C₁-C₄alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylsulfonyloxy, C₁-C₄alkylamino, C₂-C₆ dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl or C₃-C₆dialkylaminocarbonyl.

Embodiment 116

A compound of Embodiment 115 wherein each R⁷ is independently halogen,cyano, nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄alkynyl, C₃-C₆ cycloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₂-C₄alkenyloxy, C₂-C₄ alkynyloxy, C₁-C₄ alkylthio, C₁-C₄ haloalkylthio,C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl, C₁-C₄ alkylsulfonyloxy,C₁-C₄ alkylamino, C₂-C₆ dialkylamino, C₃-C₆ cycloalkylamino, C₂-C₄alkylcarbonyl, C₂-C₆ alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl or C₃-C₆dialkylaminocarbonyl.

Embodiment 117

A compound of Embodiment 116 wherein each R⁷ is independently halogen,cyano, nitro, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₃ alkenyl, C₂-C₃alkynyl, C₃-C₆ cycloalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy, C₂-C₃alkenyloxy, C₂-C₃ alkynyloxy, C₁-C₄ alkylsulfonyl, C₁-C₄haloalkylsulfonyl, C₁-C₄ alkylsulfonyloxy, C₂-C₄ alkylcarbonyl, C₂-C₆alkoxycarbonyl, C₂-C₆ alkylaminocarbonyl or C₃-C₆ dialkylaminocarbonyl.

Embodiment 118

A compound of Embodiment 117 wherein each R⁷ is independently halogen,C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₂-C₃ alkenyl, C₁-C₃ alkoxy, C₁-C₃haloalkoxy, C₂-C₄ alkylcarbonyl or C₂-C₆ alkoxycarbonyl.

Embodiment 119

A compound of Embodiment 118 wherein each R⁷ is independently halogen,methyl, trifluoromethyl or methoxy.

Embodiment 120

A compound of Embodiment 119 wherein each R⁷ is independently halogen ormethyl.

Embodiment 121

A compound of Embodiment 120 wherein each R⁷ is independently Cl, F ormethyl.

Embodiment 122

A compound of Formula 1 or any one of Embodiments 1 through 121 whereineach R⁸ is independently methyl or ethyl.

Embodiment 123

A compound of Embodiment 122 wherein R⁸ is methyl.

Embodiment 124

A compound of Formula 1 or any one of Embodiments 1 through 123 whereineach R⁹, R¹⁰ and R¹¹ is independently halogen, hydroxy, cyano, nitro,C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₁-C₄alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylsulfonyl, C₁-C₄ haloalkylsulfonyl,C₂-C₄ alkylcarbonyl, C₂-C₄ haloalkylcarbonyl, C₂-C₅ alkoxycarbonyl,C₂-C₅ alkylaminocarbonyl or C₃-C₅ dialkylaminocarbonyl.

Embodiment 125

A compound of Embodiment 124 wherein each R⁹, R¹⁰ and R¹¹ isindependently halogen, hydroxy, cyano, nitro, C₁-C₃ alkyl, C₁-C₃haloalkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy,C₁-C₃ alkylsulfonyl, C₁-C₃ haloalkylsulfonyl, C₂-C₃ alkylcarbonyl, C₂-C₃haloalkylcarbonyl, C₂-C₄ alkoxycarbonyl, C₂-C₄ alkylaminocarbonyl orC₃-C₅ dialkylaminocarbonyl.

Embodiment 126

A compound of Embodiment 125 wherein each R⁹, R¹⁰ and R¹¹ isindependently halogen, hydroxy, cyano, nitro, C₁-C₃ alkyl, C₁-C₃haloalkyl, C₁-C₃ alkoxy or C₁-C₃ haloalkoxy.

Embodiment 126a

A compound of Embodiment 126 wherein each R⁹, R¹⁰ and R¹¹ isindependently halogen, hydroxy, C₁-C₂ alkyl, C₁-C₂ haloalkyl or C₁-C₂alkoxy.

Embodiment 126b

A compound of Embodiment 126a wherein each R⁹, R¹⁰ and R¹¹ isindependently F, Cl, methyl or methoxy.

Embodiment 127

A compound of Formula 1 or any one of Embodiments 1 through 126b whereineach R¹³ is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl,C₁-C₄ alkoxy or C₁-C₄ haloalkoxy.

Embodiment 128

A compound of Embodiment 127 wherein each R¹³ is independently halogen,C₁-C₂ alkyl, C₁-C₂ haloalkyl or C₁-C₂ alkoxy.

Embodiment 129

A compound of Embodiment 128 wherein each R¹³ is independently halogenor methyl.

Embodiment 130

A compound of Embodiment 129 wherein each R¹³ is independently Cl, F,methyl or methoxy.

Embodiments of this invention, including Embodiments 1-130 above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1 but also to the starting compoundsand intermediate compounds useful for preparing the compounds ofFormula 1. In addition, embodiments of this invention, includingEmbodiments 1-130 above as well as any other embodiments describedherein, and any combination thereof, pertain to the compositions andmethods of the present invention.

Combinations of Embodiments 1-130 are illustrated by:

Embodiment A

A compound of Formula 1 wherein

-   -   R¹ is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆        alkylcarbonyl or C₂-C₆ alkoxycarbonyl, each optionally        substituted with up to 2 substituents independently selected        from R²; or phenyl optionally substituted with up to 3        substituents independently selected from R^(3a); or a 3- to        7-membered nonaromatic carbocyclic ring, wherein up to 2 carbon        atom ring members are independently selected from C(═O) and        C(═S), each ring optionally substituted with up to 3        substituents independently selected from R^(3a); or a 5- to        6-membered heterocyclic ring, each ring containing ring members        selected from carbon atoms and 1 to 4 heteroatoms independently        selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein        up to 2 carbon atom ring members are independently selected from        C(═O) and C(═S), each ring optionally substituted with up to 3        substituents independently selected from R^(3a) on carbon atom        ring members and R^(3b) on nitrogen atom ring members;    -   Z¹ is O, —NR^(4a)— or —NR^(4a)NR^(4b)—;    -   W is O;    -   Z² is —O(CH₂)_(m)— or —NR⁵N═CH—, each carbon atom optionally        substituted with up to 2 substituents independently selected        from R⁶;    -   J is phenyl optionally substituted with up to 2 substituents        independently selected from R⁷; or a 5- to 6-membered        heteroaromatic ring, each ring containing ring members selected        from carbon atoms and 1 to 4 heteroatoms independently selected        from up to 2 O, up to 2 S and up to 4 N atoms, each ring        optionally substituted with up to 2 substituents independently        selected from R⁷ on carbon atom ring members and R⁸ on nitrogen        atom ring members;    -   each R² is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄        haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₁-C₄ alkoxy,        C₁-C₄ haloalkoxy, C₂-C₄ alkylcarbonyl, C₂-C₄ haloalkylcarbonyl        or C₂-C₅ alkoxycarbonyl; or phenyl, pyridinyl, pyrazolyl,        imidazolyl, triazolyl, pyrrolidinyl, isoxazolinyl,        tetrahydrofuranyl, piperidinyl, morpholinyl or piperazinyl, each        optionally substituted with up to 2 substituents independently        selected from R^(3c) on carbon atom ring members and R^(3d) on        nitrogen atom ring members;    -   each R^(3a) and R^(3c) is independently halogen, cyano, C₁-C₂        alkyl, C₁-C₂ haloalkyl, C₂-C₃ alkenyl, C₂-C₃ alkynyl, C₁-C₂        alkoxy, C₂-C₃ alkenyloxy, C₂-C₃ alkynyloxy, C₂-C₄ alkylcarbonyl,        C₂-C₅ alkoxycarbonyl, C₂-C₅ alkylaminocarbonyl or C₃-C₇        dialkylaminocarbonyl;    -   each R^(3b) and R^(3d) is independently C₁-C₂ alkyl, C₁-C₂        alkoxy, C₂-C₃ alkylcarbonyl or C₂-C₃ alkoxycarbonyl;    -   R^(4a) and R^(4b) are each independently H, methyl, C₁-C₂        haloalkyl, methoxymethyl, methylsulfonyl, methylcarbonyl or        methoxycarbonyl; or    -   one pair of R¹ and R^(4a) substituents or one pair of R¹ and        R^(4b) substituents are taken together with the atoms to which        they are attached to form a 5- to 6-membered ring containing        ring members selected from carbon atoms and optionally up to 3        heteroatoms independently selected from up to 1 O, up to 1 S and        up to 2 N atoms, each ring optionally substituted with up to 2        substituents independently selected from R⁹; or    -   one pair of R^(3a) and R^(4a) substituents or one pair of R^(3a)        and R^(4b) substituents are taken together with the atoms to        which they are attached to form a 5- to 6-membered ring        containing ring members selected from carbon atoms and        optionally up to 3 heteroatoms independently selected from up to        1 O, up to 1 S and up to 2 N atoms, each ring optionally        substituted with up to 2 substituents independently selected        from R¹⁰; or    -   one pair of R^(3b) and R^(4a) substituents or one pair of R^(3b)        and R^(4b) substituents are taken together with the nitrogen        atoms to which they are attached to form a 5- to 6-membered ring        containing ring members selected from carbon atoms and        optionally up to 3 heteroatoms independently selected from up to        1 O, up to 1 S and up to 2 N atoms, each ring optionally        substituted with up to 2 substituents independently selected        from R¹¹;    -   R⁵ is H or methyl;    -   each R⁶ is independently halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl,        C₁-C₂ alkoxy or C₂-C₄ alkoxyalkyl; or phenyl optionally        substituted with up to 2 substituents independently selected        from R¹³;    -   each R⁷ is independently halogen, methyl, trifluoromethyl or        methoxy;    -   each R⁸ is independently methyl or ethyl;    -   each R⁹, R¹⁰ and R¹¹ is independently halogen, hydroxy, cyano,        nitro, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy or C₁-C₃        haloalkoxy; and each R¹³ is independently halogen, C₁-C₂ alkyl,        C₁-C₂ haloalkyl or C₁-C₂ alkoxy.

Embodiment B

A compound of Embodiment A wherein

-   -   R¹ is H; or C₁-C₆ alkyl, C₂-C₆ alkenyl, C₂-C₆ alkynyl, C₂-C₆        alkylcarbonyl or C₂-C₆ alkoxycarbonyl, each optionally        substituted with up to 2 substituents independently selected        from R²; or R¹ is selected from U-1 through U-79

-   -   wherein when R³ is attached to a carbon ring member, said R³ is        selected from R^(3a), and when R³ is attached to a nitrogen ring        member said R³ is selected from R^(3b); and k is 0, 1 or 2;    -   J is selected from J-1 through J-71

-   -   wherein the bond projecting to the left is bonded to Z², and the        bond projecting to the right is bonded to the oxadiazole ring in        Formula 1; each R^(7a) is independently H or R⁷; and R^(8b) is        H; provided that at most only two of R^(7a) are other than H;    -   each R² is independently halogen, cyano, C₁-C₄ alkyl, C₁-C₄        haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₁-C₄ alkoxy,        C₁-C₄ haloalkoxy, C₂-C₄ alkylcarbonyl, C₂-C₄ haloalkylcarbonyl        or C₂-C₅ alkoxycarbonyl;    -   each R^(3a) is independently halogen, C₁-C₂ alkyl, C₂-C₃        alkenyl, C₂-C₃ alkynyl, C₂-C₃ alkenyloxy, C₂-C₃ alkynyloxy,        C₂-C₄ alkylcarbonyl or C₂-C₅ alkoxycarbonyl;    -   each R^(3b) is methyl;    -   R^(4a) and R^(4b) are each independently H or methyl; or    -   one pair of R¹ and R^(4a) substituents are taken together with        the atoms to which they are attached to form a pyrazolyl or        imidazolyl ring, each ring optionally substituted with up to 2        substituents independently selected from R⁹;    -   R⁵ is H;    -   each R⁶ is independently methyl, methoxy or C₂-C₄ alkoxyalkyl;        or phenyl optionally substituted with up to 2 substituents        independently selected from R¹³;    -   each R⁷ is independently halogen or methyl;    -   each R⁹ is independently halogen, hydroxy, C₁-C₂ alkyl, C₁-C₂        haloalkyl or C₁-C₂ alkoxy; and    -   R¹³ is halogen or methyl.

Embodiment C

A compound of Embodiment B wherein

-   -   R¹ is H; or C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₂-C₄        alkylcarbonyl or C₂-C₄ alkoxycarbonyl, each optionally        substituted with up to 1 substituent selected from R²; or U-36,        U-37, U-38, U-39, U-41, U-50, U-53, U-55 or U-58;    -   Z¹ is —NR^(4a)—;    -   J is J-40, J-50, J-51 or J-52;    -   R² is halogen, cyano, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₃-C₆        cycloalkyl, C₃-C₆ halocycloalkyl, C₁-C₃ alkoxy or C₁-C₃        haloalkoxy;    -   each R^(3a) is independently halogen, C₁-C₂ alkyl, C₂-C₄        alkylcarbonyl or C₂-C₅ alkoxycarbonyl;    -   R^(4a) is H; or    -   one pair of R¹ and R^(4a) substituents are taken together with        the atoms to which they are attached to form an imidazolyl ring,        the ring optionally substituted with up to 2 substituents        independently selected from R⁹;    -   each R⁶ is independently methyl or CH₃OCH₂; or phenyl optionally        substituted with up to 1 substituent selected from R¹³;    -   each R⁷ is independently Cl, F or methyl; and    -   each R⁹ is independently F, Cl, methyl or methoxy.

Embodiment D

A compound of Embodiment C wherein

-   -   R¹ is H; or C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₂-C₄        alkylcarbonyl or C₂-C₄ alkoxycarbonyl, each optionally        substituted with up to 1 substituent selected from R²; or U-50;    -   Z² is —O(CH₂)_(m)—;    -   J is J-50;    -   R² is halogen, cyano, C₁-C₃ alkyl or C₁-C₃ alkoxy;    -   each R^(3a) is independently Br, Cl, F, methyl, C₂-C₄        alkylcarbonyl or C₂-C₄ alkoxycarbonyl;    -   R^(4a) is H;    -   each R^(7a) is H; and    -   m is 1 or 2.

Embodiment E

A compound of Embodiment D wherein

-   -   R¹ is H, C₁-C₂ alkyl, C₂-C₄ alkenyl or C₂-C₄ alkynyl; and    -   m is 1.

Embodiment F

A compound of any one of Embodiments A through C wherein

-   -   m is 3.

Specific embodiments include compounds of Formula 1 selected from thegroup consisting of:

[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methyl carbamate(Compound 17); [6-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-3-pyridinyl]methyl] carbamate;[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]-2-pyridinyl]methyl]carbamate; [5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl] carbamate;1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]ethylN-3-pyridinyl-carbamate (Compound 23);2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol- 3-yl]phenyl]ethylN-ethylcarbamate (Compound 43); and methyl2-[[4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]phenyl]methylene]-hydrazinecarboxylate (Compound 105).

This invention provides a fungicidal composition comprising a compoundof Formula 1 (including all stereoisomers, N-oxides, and salts thereof),and at least one other fungicide. Of note as embodiments of suchcompositions are compositions comprising a compound corresponding to anyof the compound embodiments described above.

This invention provides a fungicidal composition comprising a compoundof Formula 1 (including all stereoisomers, N-oxides, and salts thereof)(i.e. in a fungicidally effective amount), and at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents. Of note as embodiments of suchcompositions are compositions comprising a compound corresponding to anyof the compound embodiments described above.

This invention provides a method for controlling plant diseases causedby fungal plant pathogens comprising applying to the plant or portionthereof, or to the plant seed, a fungicidally effective amount of acompound of Formula 1 (including all stereoisomers, N-oxides, and saltsthereof). Of note as embodiments of such methods are methods comprisingapplying a fungicidally effective amount of a compound corresponding toany of the compound embodiments describe above. Of particular note areembodiments where the compounds are applied as compositions of thisinvention.

One or more of the following methods and variations as described inSchemes 1-8 can be used to prepare the compounds of Formula 1. Thedefinitions of R¹, Z¹, W, Z² and J in the compounds of Formulae 1-12below are as defined above in the Summary of the Invention unlessotherwise noted.

As shown in Scheme 1, compounds of Formula 1 can be prepared by reactingamide oximes of Formula 2 with trifluoroacetic anhydride (TFAA) or anequivalent. The reaction of Scheme 1 can be carried out without solventother than the compounds of Formula 2 and TFAA. Typically the reactionis conducted in a liquid phase with a solvent such as acetonitrile,tetrahydrofuran or toluene at a temperature between about 0 and 100° C.,optionally in the presence of a base such as pyridine or trimethylamine.Preparation of oxadiazole rings by this method and others are known inthe art; see, for example, Comprehensive Heterocyclic Chemistry, Vol. 6,Part 4B, pages 365-391, Kevin T. Potts editor, Pergamon Press, New York,1984.

As shown in Scheme 2, oximes of Formula 2 can be prepared fromcorresponding nitriles of Formula 3 and hydroxylamine or a hydroxylaminesalt (e.g., hydroxylamine hydrochloride) in a solvent such as ethanol ormethanol at temperatures generally ranging from about 0 to 80° C. A baseis needed to liberate the hydroxylamine from its salt. Suitable basesfor this reaction include, but are not limited to, sodium hydroxide,sodium bicarbonate or sodium carbonate.

As shown in Scheme 3, compounds of Formula 1 wherein Z¹ is N can also beprepared by reacting a compound of Formula 4 with an isocyanate orisothiocyanate of Formula 5 as depicted in Scheme 3. These reactions aretypically run at 0-100° C. in a solvent such as tetrahydrofuran,toluene, dichloromethane or acetonitrile in the presence of a base suchas triethylamine, diisopropylethylamine or pyridine. The method ofScheme 3 is illustrated in present Example 3, Step B.

Scheme 4 illustrates a specific example of the general method of Scheme3 for the preparation of a compound of Formula 1a (i.e. Formula 1wherein R¹ is Cl₃CC(═O)—, Z¹ is NH and Z² is —OCH₂—). In this method acompound of Formula 4a (i.e. Formula 4 wherein Z² is —OCH₂—) is reactedwith 2,2,2-trichloroacetyl isocyanate in a solvent such asdichloromethane. The method of Scheme 4 is illustrated in presentExample 4 where a compound of Formula 1a (wherein J is phenyl) isgenerated in situ.

Compounds of Formula 1a are useful for preparing other compounds ofFormula 1. For example, hydrolysis of a compound of Formula 1a usingaluminum oxide provides a compound of Formula 1 wherein R¹Z¹ is H₂N—.See present Example 4 for reaction conditions.

Alternatively, compounds of Formula 1 wherein Z¹ is N can be prepared bythe reaction of an amine of Formula 6 with a carbamoyl or thiocarbamoylchloride or imidazole of Formula 7 as shown in Scheme 5. The reaction isusually run in a solvent such as acetonitrile, dichloromethane ortetrahydrofuran at a temperature between about 0 and 80° C. When A ischlorine, the reaction is typically carried out in the presence of anacid scavenger. Typical acid scavengers include amine bases such astriethylamine, diisopropylethylamine and pyridine. Other scavengersinclude hydroxides such as sodium and potassium hydroxide and carbonatessuch as sodium carbonate and potassium carbonate. The method of Scheme 5is illustrated in Example 2.

As shown in Scheme 6, the carbamoyl or thiocarbamoyl chloride of Formula7 (wherein A is Cl) can be prepared from the corresponding hydroxy bytreatment with phosgene or thiophosgene, or their equivalents; while thecarbamoyl or thiocarbamoyl imidazole of Formula 7 (wherein A isimidazol-1-yl) can be prepared from the corresponding hydroxy bytreatment with 1,1′-carbonyldiimidazole or 1,1′-thiocarbonyldiimidazole,according to general methods known in the art. Also, present Example 1,Step B illustrates the method of Scheme 6 for a compound of Formula 7wherein A is imidazol-1-yl.

As shown in Scheme 7, the compounds of Formula 8 can be prepared byreaction of nitriles of Formula 9 with hydroxylamine to give the amideoximes of Formula 10 using conditions analogous to those described inScheme 2. Treatment of compounds of Formula 10 with trifluoroaceticanhydride, analogous to the transformation depicted in Scheme 1,provides compounds of Formula 8. The nitriles of Formula 5 are known orcan be prepared by one skilled in the art. The method of Scheme 7 isillustrated in present Example 1, Step A.

As shown in Scheme 8, compounds of Formula 1 wherein Z² is —NR⁵N═CH— canbe prepared by reaction of an aldehyde of Formula 11 with acarbohydrazide of Formula 12.

The reaction is typically run in a solvent such as methanol or ethanolat a temperature between 0 to 80° C.

Analogous to the method of Scheme 8, compounds of Formula 4 (see Scheme3) wherein Z² is —NR⁵N═CH— can be prepared from aldehydes Formula 11 andhydrazines of formula R⁵NHNH₂. Aldehydes of Formula 11 are known or canbe prepared by methods analogous to those reported for in WO 2017055473(see preparation of4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3-yl]benzaldehyde).

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula 1 may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, T. W. Greene and P. G. M. Wuts, Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula 1. One skilled in the artwill also recognize that it may be necessary to perform a combination ofthe steps illustrated in the above schemes in an order other than thatimplied by the particular sequence presented to prepare the compounds ofFormula 1.

One skilled in the art will also recognize that compounds of Formula 1and the intermediates described herein can be subjected to variouselectrophilic, nucleophilic, radical, organometallic, oxidation, andreduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Steps in the following Examples illustrate a procedure foreach step in an overall synthetic transformation, and the startingmaterial for each step may not have necessarily been prepared by aparticular preparative run whose procedure is described in otherExamples or Steps. Percentages are by weight except for chromatographicsolvent mixtures or where otherwise indicated. Parts and percentages forchromatographic solvent mixtures are by volume unless otherwiseindicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane; ¹⁹F NMR spectra are reported in ppm usingtrichlorofluoromethane as reference; “s” means singlet, “d” meansdoublet, “m” means multiplet, “br s” means broad singlet and “br m”means broad multiplet.

Example 1 Preparation of2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl-1H-imidazole-1-carboxylate(Compound 40) Step A: Preparation of4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzeneethanol

A mixture of 4-(2-hydroxyethyl)benzonitrile (10.0 g, 68 mmol) andhydroxylamine (50% aqueous solution, 8.4 mL, 136 mmol) in absoluteethanol (50 mL) was stirred at ambient temperature for 16 h, and thenconcentrated under reduced pressure. The resulting material was dilutedwith acetonitrile (100 mL) and concentrated under reduced pressure (2×),and the resulting solid was slurried in diethyl ether and filtered toprovide N′-hydroxy-4-(2-hydroxyethyl)benzamidine (11.9 g) as a whitesolid.

To a mixture of N′-hydroxy-4-(2-hydroxyethyl)benzamidine (11.7 g, 65.4mmol) and pyridine (12.1 mL, 150 mmol) in acetonitrile (100 mL) at 0° C.was added trifluoroacetic anhydride (20.8 mL, 140 mmol) dropwise over 30minutes. The reaction mixture was heated at 70° C. After 4 h, thereaction mixture was cooled to ambient temperature, and then added toice water (700 mL) and allowed to stir for 3 days. The mixture wasextracted with ethyl acetate (3×100 mL) and the combined extracts werewashed with aqueous hydrochloric acid solution (1 N), saturated aqueoussodium bicarbonate solution and saturated aqueous sodium chloridesolution. The mixture was then dried over magnesium sulfate, filteredand concentrated under reduced pressure to provide an orange solid (17.7g). The orange solid was stirred in hexane (100 mL) for 2 hr, filteredand air dried to give the title compound as a light yellow solid (10.65g).

¹H NMR (CDCl₃): δ 1.35-1.50 (br s, 1H), 2.96 (m, 2H), 3.93 (m, 2H), 7.40(m, 2H), 8.07 (m, 2H);

¹⁹F NMR (CDCl₃): δ−65.38.

The following compounds were prepared analogous to the method Step A ofExample 1:

-   4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenemethanol.

¹H NMR (CDCl₃): δ 1.80 (m, 1H), 4.80-4.81 (d, 2H), 7.54 (d, 2H), 8.13(d, 2H);

¹⁹F NMR (CDCl₃): δ−65.37.

-   4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenepropanol.

¹H NMR (CDCl₃): δ 1.92-1.95 (m, 2H), 2.79-2.81 (m, 2H), 3.69-3.72 (m,2H), 7.35-7.37 (d, 2H), 8.03-8.04 (d, 2H);

¹⁹F NMR (CDCl₃): δ−65.37.

Step B: Preparation of2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl-1H-imidazole-1-carboxylate

A mixture of 1,1′-carbonyldiimidazole (CDI) (2.0 g, 12.3 mmol) inacetonitrile (25 mL) was cooled to 0° C. in an ice/water bath, and thena solution of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzeneethanol(i.e. the product of Step A) (2.58 g, 10 mmol) in acetonitrile (20 mL)was added dropwise. The reaction mixture was allowed to warm to ambienttemperature, stirred overnight, and then concentrated under reducedpressure. The resulting material was diluted with dichloromethane,washed with water and saturated aqueous sodium chloride solution, driedover magnesium sulfate, filtered and concentrated under reduced pressureto provide the title compound, a compound of the present invention, as atan solid (3.54 g).

¹H NMR (CDCl₃): δ 3.20 (m, 2H), 4.67 (m, 2H), 7.06 (s, 1H), 7.37 (s,1H), 7.42 (m, 2H), 8.09 (m, 3H);

¹⁹F NMR (CDCl₃): δ−65.38.

The following compound was prepared analogous to the method Step B ofExample 1:

-   2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl-1H-imidazole-1-carboxylate    (Compound 8).

¹H NMR (CDCl₃): δ 5.50 (s, 2H), 7.09 (s, 1H), 7.46 (s, 1H), 7.60 (m,2H), 8.18 (m, 3H) (m, 3H);

¹⁹F NMR (CDCl₃): δ−65.33.

Example 2 Preparation of2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethylN-ethylcarbamate (Compound 43)

2-[4-[5-(Trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl-1H-imidazole-1-carboxylat3(i.e. the product of Step B) (300 mg, 0.85 mmol) was dissolved in asolution of ethylamine (2 M in tetrahydrofuran, 2 mL) and stirred atambient temperature for 2 hr. The reaction mixture was concentratedunder reduced pressure and the resulting material was diluted withdichloromethane. The dichloromethane mixture was washed with aqueoushydrochloric acid solution (1 N), dried over magnesium sulfate, filteredand concentrated under reduced pressure to provide the title compound, acompound of the present invention, as a white solid (0.27 g).

¹H NMR (CDCl₃): δ 1.13 (m, 3H), 3.01 (m, 2H), 3.20 (m, 2H), 4.32 (m,2H), 4.62 (br s, 1H), 7.38 (m, 2H), 8.05 (m, 3H);

¹⁹F NMR (CDCl₃): δ−65.39.

Example 3 Preparation of1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethylN-3-pyridinylcarbamate (Compound 23) Step A: Preparation ofα-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenemethanol

To a mixture of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzaldehyde(1.53 g, 6.3 mmol) in tetrahydrofuran (20 ml) at −12° C. was added asolution of methylmagnesium bromide (3 M in diethyl ether, 2.1 mL, 6.3mmol) dropwise. The reaction mixture was stirred for 2 h at −12° C., andthen quenched with saturated aqueous ammonium chloride solution. Theresulting mixture was poured into water and extracted with ethylacetate. The organic extracts were washed with saturated aqueous sodiumchloride solution, dried over sodium sulfate, filtered and concentratedunder reduced pressure. The resulting material was purified by silicagel chromatography (eluting with a gradient of 5 to 50% ethyl acetate inhexanes) to provide the title compound as a solid (1.63 g).

¹H NMR (CDCl₃): δ 1.40-1.61 (m, 3H), 4.84-5.06 (m, 1H), 7.50 (d, 2H),8.06 (d, 2H);

¹⁹F NMR (CDCl₃): δ−65.49.

Step B: Preparation of1-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethylN-3-pyridinylcarbamate

To a solution ofα-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenemethanol(i.e. the product of Step A) (0.287 g, 1.11 mmol) in acetonitrile (10mL) was added triethylamine (0.25 mL, 1.8 mmol) followed by3-isocyanatopyridine (0.24 g, 2 mmol). The reaction mixture was heatedat reflux for 1 h, cooled to ambient temperature, and then concentratedunder reduced pressure. The resulting material was purified by silicagel chromatography (eluting with a gradient of 0 to 100% ethyl acetatein hexanes) to provide the title compound, a compound of the presentinvention, as a white solid (0.30 g).

1H NMR (CDCl₃): δ 1.64 (d, 3H), 5.96 (m, 1H), 7.23-7.26 (m, 1H),7.45-7.58 (m, 3H), 8.02 (m, 1H), 8.10-8.12 (d, 2H), 8.32-8.34 (m, 1H),8.52-8.54 (m, 1H);

¹⁹F NMR (CDCl₃): δ−65.35.

Example 4 Preparation of[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl carbamate(Compound 17)

To a mixture of4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenemethanol (preparedanalogous to the method of Step A in Example 1) (36 g, 147 mmol) indichloromethane (600 mL) was added 2,2,2-trichloroacetyl isocyanate(33.3 g, 177 mmol) while maintaining the reaction temperature below 30°C. The reaction mixture was stirred for 2 h at ambient temperature toprovide a reaction mixture containing the compound2,2,2-trichloro-1-((2-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)acetyl)-λ²azaneyl)ethan-1-one(a compound of the present invention). Aluminum oxide (720 g) was addedto the reaction mixture portionwise and stirring was continuedovernight. The reaction mixture was filtered, rinsing with ethylacetate, and the filtrate was concentrated under reduced pressure toprovide a white solid (41 g). The white solid was crystallized fromethanol to provide the title compound, a compound of the presentinvention, as colorless prisms melting at 142-144° C.

¹H NMR (CDCl₃): δ 4.59-4.88 (br s, 2H), 5.19 (s, 2H) 7.51-7.52 (m, 2H),8.11-8.13 (m, 2H);

¹⁹F NMR (CDCl₃): δ−65.35.

Example 5

Preparation of methyl2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methylene]-hydrazinecarboxylate(Compound 105)

To a mixture of 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzaldehyde(0.80 g, 3.30 mmol) in methanol (10 mL) was added methylhydrazinocarboxylate (0.307 g, 3.30 mmol). The reaction mixture wasstirred at ambient temperature, and then concentrated under reducedpressure. The resulting material was purified by MPLC silica gelchromatography (eluting with a gradient of 0 to 100% ethyl acetate inhexanes) to provide a white solid (0.84 g). The white solid wascrystallized from ethanol to provide the title compound, a compound ofthe present invention, as colorless needles (549 mg) melting at 183-185°C.

¹H NMR (CDCl₃): δ 3.89 (br s, 3H), 7.83-7.85 (m, 2H), 7.9-8.0 (br s,1H), 8.13-8.15 (m, 2H), 8.2-8.5 (br s, 1H);

¹⁹F NMR (CDCl₃): δ−65.34.

Formulation/Utility

A compound of Formula 1 of this invention (including N-oxides, hydrates,and salts thereof) will generally be used as a fungicidal activeingredient in a composition, i.e. formulation, with at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents, which serve as a carrier. Theformulation or composition ingredients are selected to be consistentwith the physical properties of the active ingredient, mode ofapplication and environmental factors such as soil type, moisture andtemperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions and/or suspoemulsions)and the like, which optionally can be thickened into gels. The generaltypes of aqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsionand suspo-emulsion. The general types of nonaqueous liquid compositionsare emulsifiable concentrate, microemulsifiable concentrate, dispersibleconcentrate and oil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, pills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying. Such liquid and solid formulations are formulated to bereadily diluted in the spray medium, usually water, but occasionallyanother suitable medium like an aromatic or paraffinic hydrocarbon orvegetable oil. Spray volumes can range from about one to severalthousand liters per hectare, but more typically are in the range fromabout ten to several hundred liters per hectare. Sprayable formulationscan be tank mixed with water or another suitable medium for foliartreatment by aerial or ground application, or for application to thegrowing medium of the plant. Liquid and dry formulations can be metereddirectly into drip irrigation systems or metered into the furrow duringplanting. Liquid and solid formulations can be applied onto seeds ofcrops and other desirable vegetation as seed treatments before plantingto protect developing roots and other subterranean plant parts and/orfoliage through systemic uptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersible0.001-90 0-99.999 0-15 and Water-soluble Granules, Tablets and Powders.Oil Dispersions,    1-50 40-99    0-50 Suspensions, Emulsions, Solutions(including Emulsifiable Concentrates) Dusts    1-25 70-99    0-5 Granules and Pellets 0.001-95 5-99.999 0-15 High Strength Compositions  90-99 0-10    0-2 

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates(e.g., triethyl phosphate), ethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, polypropylene glycol, propylenecarbonate, butylene carbonate, paraffins (e.g., white mineral oils,normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes,glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons,dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones suchas cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexylacetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetateand isobornyl acetate, other esters such as alkylated lactate esters,dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, andalcohols, which can be linear, branched, saturated or unsaturated, suchas methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutylalcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecylalcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecylalcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol,diacetone alcohol, cresol and benzyl alcohol. Liquid diluents alsoinclude glycerol esters of saturated and unsaturated fatty acids(typically C₆-C₂₂), such as plant seed and fruit oils (e.g., oils ofolive, castor, linseed, sesame, corn (maize), peanut, sunflower,grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palmkernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, codliver oil, fish oil), and mixtures thereof. Liquid diluents also includealkylated fatty acids (e.g., methylated, ethylated, butylated) whereinthe fatty acids may be obtained by hydrolysis of glycerol esters fromplant and animal sources, and can be purified by distillation. Typicalliquid diluents are described in Marsden, Solvents Guide, 2nd Ed.,Interscience, New York, 1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyl peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquaternary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids.Such formulation auxiliaries and additives may control: pH (buffers),foaming during processing (antifoams such polyorganosiloxanes (e.g.,Rhodorsil® 416)), sedimentation of active ingredients (suspendingagents), viscosity (thixotropic thickeners), in-container microbialgrowth (antimicrobials), product freezing (antifreezes), color(dyes/pigment dispersions (e.g., Pro-lzed® Colorant Red)), wash-off(film formers or stickers), evaporation (evaporation retardants), andother formulation attributes. Film formers include, for example,polyvinyl acetates, polyvinyl acetate copolymers,polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols,polyvinyl alcohol copolymers and waxes. Examples of formulationauxiliaries and additives include those listed in McCutcheon's Volume 2:Functional Materials, annual International and North American editionspublished by McCutcheon's Division, The Manufacturing ConfectionerPublishing Co.; and PCT Publication WO 03/024222.

The compound of Formula 1 and any other active ingredients are typicallyincorporated into the present compositions by dissolving the activeingredient in a solvent or by grinding in a liquid or dry diluent.Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 m can be wet milled using media mills to obtainparticles with average diameters below 3 μm. Aqueous slurries can bemade into finished suspension concentrates (see, for example, U.S. Pat.No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 mrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. Nos.4,144,050, 3,920,442 and DE 3,246,493. Tablets can be prepared as taughtin U.S. Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can beprepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

One embodiment of the present invention relates to a method forcontrolling fungal pathogens, comprising diluting the fungicidalcomposition of the present invention (a compound of Formula 1 formulatedwith surfactants, solid diluents and liquid diluents or a formulatedmixture of a compound of Formula 1 and at least one other fungicide)with water, and optionally adding an adjuvant to form a dilutedcomposition, and contacting the fungal pathogen or its environment withan effective amount of said diluted composition.

Although a spray composition formed by diluting with water a sufficientconcentration of the present fungicidal composition can providesufficient efficacy for controlling fungal pathogens, separatelyformulated adjuvant products can also be added to spray tank mixtures.These additional adjuvants are commonly known as “spray adjuvants” or“tank-mix adjuvants”, and include any substance mixed in a spray tank toimprove the performance of a pesticide or alter the physical propertiesof the spray mixture. Adjuvants can be anionic or nonionic surfactants,emulsifying agents, petroleum-based crop oils, crop-derived seed oils,acidifiers, buffers, thickeners or defoaming agents. Adjuvants are usedto enhancing efficacy (e.g., biological availability, adhesion,penetration, uniformity of coverage and durability of protection), orminimizing or eliminating spray application problems associated withincompatibility, foaming, drift, evaporation, volatilization anddegradation. To obtain optimal performance, adjuvants are selected withregard to the properties of the active ingredient, formulation andtarget (e.g., crops, insect pests).

The amount of adjuvants added to spray mixtures is generally in therange of about 2.5% to 0.1% by volume. The application rates ofadjuvants added to spray mixtures are typically between about 1 to 5 Lper hectare. Representative examples of spray adjuvants include: Adigor®(Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet®(Helena Chemical Company) polyalkyleneoxide modifiedheptamethyltrisiloxane and Assist® (BASF) 17% surfactant blend in 83%paraffin based mineral oil.

One method of seed treatment is by spraying or dusting the seed with acompound of the invention (i.e. as a formulated composition) beforesowing the seeds. Compositions formulated for seed treatment generallycomprise a film former or adhesive agent.

Therefore, typically a seed coating composition of the present inventioncomprises a biologically effective amount of a compound of Formula 1 anda film former or adhesive agent. Seeds can be coated by spraying aflowable suspension concentrate directly into a tumbling bed of seedsand then drying the seeds. Alternatively, other formulation types suchas wetted powders, solutions, suspoemulsions, emulsifiable concentratesand emulsions in water can be sprayed on the seed. This process isparticularly useful for applying film coatings on seeds. Various coatingmachines and processes are available to one skilled in the art. Suitableprocesses include those listed in P. Kosters et al., Seed Treatment:Progress and Prospects, 1994 BCPC Mongraph No. 57, and references listedtherein.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox-Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, U K, 2000.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Compound numbers referto compounds in Index Tables A-G. Without further elaboration, it isbelieved that one skilled in the art using the preceding description canutilize the present invention to its fullest extent. The followingExamples are, therefore, to be constructed as merely illustrative, andnot limiting of the disclosure in any way whatsoever.

Example A High Strength Concentrate Compound 17 98.5% silica aerogel0.5% synthetic amorphous fine silica 1.0% Example B Wettable PowderCompound 67 65.0% dodecylphenol polyethylene glycol ether 2.0% sodiumligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite(calcined) 23.0% Example C Granule Compound 63 10.0% attapulgitegranules (low 90.0% volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50sieves) Example D Extruded Pellet Compound 61 25.0% anhydrous sodiumsulfate 10.0% crude calcium ligninsulfonate 5.0% sodiumalkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0% ExampleE Emulsifiable Concentrate Compound 52 10.0% polyoxyethylene sorbitolhexoleate 20.0% C₆-C₁₀ fatty acid methyl ester 70.0% Example FMicroemulsion Compound 51 5.0% polyvinylpyrrolidone-vinyl acetatecopolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water20.0% Example G Seed Treatment Compound 47 20.00%polyvinylpyrrolidone-vinyl acetate copolymer 5.00% montan acid wax 5.00%calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene blockcopolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20%colorant red dye 0.05% water 65.75% Example H Fertilizer Stick Compound117 2.50% pyrrolidone-styrene copolymer 4.80% tristyrylphenyl16-ethoxylate 2.30% talc 0.80% corn starch 5.00% slow-release fertilizer36.00% kaolin 38.00% water 10.60% Example I Suspension ConcentrateCompound 118  35% butyl polyoxyethylene/polypropylene block copolymer4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylicpolymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone baseddefoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% water 53.7%  Example JEmulsion in Water Compound 20 10.0% butyl polyoxyethylene/polypropyleneblock copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0%styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% aromaticpetroleum based hydrocarbon 20.0 water 58.7% Example K Oil DispersionCompound 17 25% polyoxyethylene sorbitol hexaoleate 15% organicallymodified bentonite clay 2.5%  fatty acid methyl ester 57.5%  Example LSuspoemulsion Compound 9 10.0% imidacloprid 5.0% butylpolyoxyethylene/polypropylene block copolymer 4.0% stearicacid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0%xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%1,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon20.0% water 53.7%

Water-soluble and water-dispersible formulations are typically dilutedwith water to form aqueous compositions before application. Aqueouscompositions for direct applications to the plant or portion thereof(e.g., spray tank compositions) typically contain at least about 1 ppmor more (e.g., from 1 ppm to 100 ppm) of the compound(s) of thisinvention.

Seed is normally treated at a rate of from about 0.001 g (more typicallyabout 0.1 g) to about 10 g per kilogram of seed (i.e. from about 0.0001to 1% by weight of the seed before treatment). A flowable suspensionformulated for seed treatment typically comprises from about 0.5 toabout 70% of the active ingredient, from about 0.5 to about 30% of afilm-forming adhesive, from about 0.5 to about 20% of a dispersingagent, from 0 to about 5% of a thickener, from 0 to about 5% of apigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0to about 1% of a preservative, and from 0 to about 75% of a volatileliquid diluent.

The compounds of this invention are useful as plant disease controlagents. The present invention therefore further comprises a method forcontrolling plant diseases caused by fungal plant pathogens comprisingapplying to the plant or portion thereof to be protected, or to theplant seed to be protected, an effective amount of a compound of theinvention or a fungicidal composition containing said compound. Thecompounds and/or compositions of this invention provide control ofdiseases caused by a broad spectrum of fungal plant pathogens in theAscomycota, Basidiomycota, Zygomycota phyla, and the fungal-likeOomycata class. They are effective in controlling a broad spectrum ofplant diseases, particularly foliar pathogens of ornamental, turf,vegetable, field, cereal, and fruit crops. These pathogens include butare not limited to those listed in Table 1-1. For Ascomycetes andBasidiomycetes, names for both the sexual/teleomorph/perfect stage aswell as names for the asexual/anamorph/imperfect stage (in parentheses)are listed where known. Synonymous names for pathogens are indicated byan equal sign. For example, the sexual/teleomorph/perfect stage namePhaeosphaeria nodorum is followed by the correspondingasexual/anamorph/imperfect stage name Stagnospora nodorum and thesynonymous older name Septoria nodorum.

TABLE 1-1 Ascomycetes in the order Pleosporales including Alternariasolani, A. altemata and A. brassicae, Guignardia bidwellii, Venturiainaequalis, Pyrenophora tritici-repentis (Dreschlera tritici-repentis =Helminthosporium tritici-repentis) and Pyrenophora teres (Dreschlerateres = Helminthosporium teres), Corynespora cassiicola, Phaeosphaerianodorum (Stagonospora nodorum = Septoria nodorum), Cochliobolus carbonumand C. heterostrophus, Leptosphaeria biglobosa and L. maculans;Ascomycetes in the order Mycosphaerellales including Mycosphaerellagraminicola (Zymoseptoria tritici = Septoria tritici), M. berkeleyi(Cercosporidium personatum), M. arachidis (Cercospora arachidicola),Passalora sojina (Cercospora sojina), Cercospora zeae-maydis and C.beticola; Ascomycetes in the order Erysiphales (the powdery mildews)such as Blumeria graminis f.sp. tritici and Blumeria graminis f.sp.hordei, Erysiphe polygoni, E. necator (=Uncinula necator), Podosphaerafuliginea (=Sphaerotheca fuliginea), and Podosphaera leucotricha(=Sphaerotheca fuliginea); Ascomycetes in the order Helotiales such asBotryotinia fuckeliana (Botrytis cinerea), Oculimacula yallundae(=Tapesia yallundae; anamorph Helgardia herpotrichoides =Pseudocercosporella herpetrichoides), Monilinia fructicola, Sclerotiniasclerotiorum, Sclerotinia minor, and Sclerotinia homoeocarpa;Ascomycetes in the order Hypocreales such as Giberella zeae (Fusariumgraminearum), G. monoliformis (Fusarium moniliforme), Fusarium solaniand Verticillium dahliae; Ascomycetes in the order Eurotiales such asAspergillus flavus and A. parasiticus; Ascomycetes in the orderDiaporthales such as Cryptosphorella viticola (=Phomopsis viticola),Phomopsis longicolla, and Diaporthe phaseolorum; Other Ascomycetepathogens including Magnaporthe grisea, Gaeumannomyces graminis,Rhynchosporium secalis, and anthracnose pathogens such as Glomerellaacutata (Colletotrichum acutatum), G. graminicola (C. graminicola) andG. lagenaria (C. orbiculare); Basidiomycetes in the order Urediniales(the rusts) including Puccinia recondita, P. striiformis, Pucciniahordei, P. graminis and P. arachidis), Hemileia vastatrix and Phakopsorapachyrhizi; Basidiomycetes in the order Ceratobasidiales such asThanatophorum cucumeris (Rhizoctonia solani) and Ceratobasidiumoryzae-sativae (Rhizoctonia oryzae); Basidiomycetes in the orderPolyporales such as Athelia rolfsii (Sclerotium rolfsii); Basidiomycetesin the order Ustilaginales such as Ustilago maydis; Zygomycetes in theorder Mucorales such as Rhizopus stolonifer, Oomycetes in the orderPythiales, including Phytophthora infestans, P. megasperma, P.parasitica, P. sojae, P. cinnamomi and P. capsici, and Pythium pathogenssuch as Pythium aphanidermatum, P. graminicola, P. irregulare, P.ultimum and P. dissoticum; Oomycetes in the order Peronosporales such asPlasmopara viticola, P. halstedii, Peronospora hyoscyami (=Peronosporatabacina), P. manshurica, Hyaloperonospora parasitica (=Peronosporaparasitica), Pseudoperonospora cubensis and Bremia lactucae; and othergenera and species closely related to all of the above pathogens.

In addition to their fungicidal activity, the compositions orcombinations also have activity against bacteria such as Erwiniaamylovora, Xanthomonas campestris, Pseudomonas syringae, and otherrelated species. By controlling harmful microorganisms, the compounds ofthe invention are useful for improving (i.e. increasing) the ratio ofbeneficial to harmful microorganisms in contact with crop plants ortheir propagules (e.g., seeds, corms, bulbs, tubers, cuttings) or in theagronomic environment of the crop plants or their propagules.

Compounds of the invention are useful in treating all plants, plantparts and seeds. Plant and seed varieties and cultivars can be obtainedby conventional propagation and breeding methods or by geneticengineering methods. Genetically modified plants or seeds (transgenicplants or seeds) are those in which a heterologous gene (transgene) hasbeen stably integrated into the plant's or seed's genome. A transgenethat is defined by its particular location in the plant genome is calleda transformation or transgenic event.

Genetically modified plant cultivars which can be treated according tothe invention include those that are resistant against one or morebiotic stresses (pests such as nematodes, insects, mites, fungi, etc.)or abiotic stresses (drought, cold temperature, soil salinity, etc.), orthat contain other desirable characteristics. Plants can be geneticallymodified to exhibit traits of, for example, herbicide tolerance,insect-resistance, modified oil profiles or drought tolerance.

Treatment of genetically modified plants and seeds with compounds of theinvention may result in super-additive or synergistic effects. Forexample, reduction in application rates, broadening of the activityspectrum, increased tolerance to biotic/abiotic stresses or enhancedstorage stability may be greater than expected from just simple additiveeffects of the application of compounds of the invention on geneticallymodified plants and seeds.

Compounds of this invention are useful in seed treatments for protectingseeds from plant diseases. In the context of the present disclosure andclaims, treating a seed means contacting the seed with a biologicallyeffective amount of a compound of this invention, which is typicallyformulated as a composition of the invention. This seed treatmentprotects the seed from soil-borne disease pathogens and generally canalso protect roots and other plant parts in contact with the soil of theseedling developing from the germinating seed. The seed treatment mayalso provide protection of foliage by translocation of the compound ofthis invention or a second active ingredient within the developingplant. Seed treatments can be applied to all types of seeds, includingthose from which plants genetically transformed to express specializedtraits will germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensistoxin or those expressing herbicide resistance such as glyphosateacetyltransferase, which provides resistance to glyphosate. Seedtreatments with compounds of this invention can also increase vigor ofplants growing from the seed.

Compounds of this invention and their compositions, both alone and incombination with other fungicides, nematicides and insecticides, areparticularly useful in seed treatment for crops including, but notlimited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats,barley, rye and rice), potatoes, vegetables and oilseed rape.

Furthermore, the compounds of this invention are useful in treatingpostharvest diseases of fruits and vegetables caused by fungi andbacteria. These infections can occur before, during and after harvest.For example, infections can occur before harvest and then remain dormantuntil some point during ripening (e.g., host begins tissue changes insuch a way that infection can progress); also infections can arise fromsurface wounds created by mechanical or insect injury. In this respect,the compounds of this invention can reduce losses (i.e. losses resultingfrom quantity and quality) due to postharvest diseases which may occurat any time from harvest to consumption. Treatment of postharvestdiseases with compounds of the invention can increase the period of timeduring which perishable edible plant parts (e.g., fruits, seeds,foliage, stems, bulbs, tubers) can be stored refrigerated orun-refrigerated after harvest, and remain edible and free fromnoticeable or harmful degradation or contamination by fungi or othermicroorganisms. Treatment of edible plant parts before or after harvestwith compounds of the invention can also decrease the formation of toxicmetabolites of fungi or other microorganisms, for example, mycotoxinssuch as aflatoxins.

Plant disease control is ordinarily accomplished by applying aneffective amount of a compound of this invention either pre- orpost-infection, to the portion of the plant to be protected such as theroots, stems, foliage, fruits, seeds, tubers or bulbs, or to the media(soil or sand) in which the plants to be protected are growing. Thecompounds can also be applied to seeds to protect the seeds andseedlings developing from the seeds. The compounds can also be appliedthrough irrigation water to treat plants. Control of postharvestpathogens which infect the produce before harvest is typicallyaccomplished by field application of a compound of this invention, andin cases where infection occurs after harvest the compounds can beapplied to the harvested crop as dips, sprays, fumigants, treated wrapsand box liners.

Rates of application for these compounds (i.e. a fungicidally effectiveamount) can be influenced by factors such as the plant diseases to becontrolled, the plant species to be protected, ambient moisture andtemperature and should be determined under actual use conditions. Oneskilled in the art can easily determine through simple experimentationthe fungicidally effective amount necessary for the desired level ofplant disease control.

Foliage can normally be protected when treated at a rate of from lessthan about 1 g/ha to about 5,000 g/ha of active ingredient. Seed andseedlings can normally be protected when seed is treated at a rate offrom about 0.001 g (more typically about 0.1 g) to about 10 g perkilogram of seed.

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including fungicides,insecticides, nematocides, bactericides, acaricides, herbicides,herbicide safeners, growth regulators such as insect molting inhibitorsand rooting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, plant nutrients, otherbiologically active compounds or entomopathogenic bacteria, virus orfungi to form a multi-component pesticide giving an even broaderspectrum of agricultural protection. Thus the present invention alsopertains to a composition comprising a compound of Formula 1 (in afungicidally effective amount) and at least one additional biologicallyactive compound or agent (in a biologically effective amount) and canfurther comprise at least one of a surfactant, a solid diluent or aliquid diluent. The other biologically active compounds or agents can beformulated in compositions comprising at least one of a surfactant,solid or liquid diluent. For mixtures of the present invention, one ormore other biologically active compounds or agents can be formulatedtogether with a compound of Formula 1, to form a premix, or one or moreother biologically active compounds or agents can be formulatedseparately from the compound of Formula 1, and the formulations combinedtogether before application (e.g., in a spray tank) or, alternatively,applied in succession.

As mentioned in the Summary of the Invention, one aspect of the presentinvention is a fungicidal composition comprising (i.e. a mixture orcombination of) a compound of Formula 1, an N-oxide, or a salt thereof(i.e. component a), and at least one other fungicide (i.e. component b).Of note is such a combination where the other fungicidal activeingredient has different site of action from the compound of Formula 1.In certain instances, a combination with at least one other fungicidalactive ingredient having a similar spectrum of control but a differentsite of action will be particularly advantageous for resistancemanagement. Thus, a composition of the present invention can furthercomprise a fungicidally effective amount of at least one additionalfungicidal active ingredient having a similar spectrum of control but adifferent site of action.

Of note is a composition which in addition to the Formula 1 compound ofcomponent (a), includes as component (b) at least one fungicidalcompound selected from the group consisting of the FRAC-defined mode ofaction (MOA) classes (A) nucleic acid synthesis, (B) mitosis and celldivision, (C) respiration, (D) amino acid and protein synthesis, (E)signal transduction, (F) lipid synthesis and membrane integrity, (G)sterol biosynthesis in membranes, (H) cell wall biosynthesis inmembranes, (I) melanin synthesis in cell wall, (P) host plant defenseinduction, multi-site contact activity and unknown mode of action.

FRAC-recognized or proposed target sites of action along with their FRACtarget site codes belonging to the above MOA classes are (A1) RNApolymerase I, (A2) adenosine deaminase, (A3) DNA/RNA synthesis(proposed), (A4) DNA topoisomerase, (B1-B3) β-tubulin assembly inmitosis, (B4) cell division (proposed), (B5) delocalization ofspectrin-like proteins, (C1) complex I NADH odxido-reductase, (C2)complex II: succinate dehydrogenase, (C3) complex III: cytochrome bcl(ubiquinol oxidase) at Qo site, (C4) complex III: cytochrome bcl(ubiquinone reductase) at Qi site, (C5) uncouplers of oxidativephosphorylation, (C6) inhibitors of oxidative phosphorylation, ATPsynthase, (C7) ATP production (proposed), (C8) complex III: cytochromebcl (ubiquinone reductase) at Qx (unknown) site, (D1) methioninebiosynthesis (proposed), (D2-D5) protein synthesis, (E1) signaltransduction (mechanism unknown), (E2-E3) MAP/histidine kinase inosmotic signal transduction, (F2) phospholipid biosynthesis, methyltransferase, (F3) lipid peroxidation (proposed), (F4) cell membranepermeability, fatty acids (proposed), (F6) microbial disrupters ofpathogen cell membranes, (F7) cell membrane disruption (proposed), (G1)C14-demethylase in sterol biosynthesis, (G2) Δ14-reductase andΔ8→Δ7-isomerase in sterol biosynthesis, (G3) 3-keto reductase,C4-demethylation, (G4) squalene epoxidase in sterol biosynthesis, (H3)trehalase and inositol biosynthesis, (H4) chitin synthase, (H5)cellulose synthase, (I1) reductase in melanin biosynthesis and (I2)dehydratase in melanin biosynthesis.

Of particular note is a composition which in addition to the Formula 1compound of component (a), includes as component (b) at least onefungicidal compound selected from the group consisting of the classes(b1) methyl benzimidazole carbamate (MBC) fungicides; (b2) dicarboximidefungicides; (b3) demethylation inhibitor (DMI) fungicides; (b4)phenylamide fungicides; (b5) amine/morpholine fungicides; (b6)phospholipid biosynthesis inhibitor fungicides; (b7) succinatedehydrogenase inhibitor fungicides; (b8) hydroxy(2-amino-)pyrimidinefungicides; (b9) anilinopyrimidine fungicides; (b10)N-phenyl carbamatefungicides; (b11) quinone outside inhibitor (QoI) fungicides; (b12)phenylpyrrole fungicides; (b13) azanaphthalene fungicides; (b14) lipidperoxidation inhibitor fungicides; (b15) melanin biosynthesisinhibitor-reductase (MBI-R) fungicides; (b16) melanin biosynthesisinhibitor-dehydratase (MBI-D) fungicides; (b17) sterol biosynthesisinhibitor (SBI): Class III fungicides; (b18) squalene-epoxidaseinhibitor fungicides; (b19) polyoxin fungicides; (b20) phenylureafungicides; (b21) quinone inside inhibitor (QiI) fungicides; (b22)benzamide and thiazole carboxamide fungicides; (b23) enopyranuronic acidantibiotic fungicides; (b24) hexopyranosyl antibiotic fungicides; (b25)glucopyranosyl antibiotic: protein synthesis fungicides; (b26)glucopyranosyl antibiotic: trehalase and inositol biosynthesisfungicides; (b27) cyanoacetamideoxime fungicides; (b28) carbamatefungicides; (b29) oxidative phosphorylation uncoupling fungicides; (b30)organo tin fungicides; (b31) carboxylic acid fungicides; (b32)heteroaromatic fungicides; (b33) phosphonate fungicides; (b34)phthalamic acid fungicides; (b35) benzotriazine fungicides; (b36)benzene-sulfonamide fungicides; (b37) pyridazinone fungicides; (b38)thiophene-carboxamide fungicides; (b39) complex I NADH oxidoreductaseinhibitor fungicides; (b40) carboxylic acid amide (CAA) fungicides;(b41) tetracycline antibiotic fungicides; (b42) thiocarbamatefungicides; (b43) benzamide fungicides; (b44) microbial fungicides;(b45) Q_(X)I fungicides; (b46) plant extract fungicides; (b47) hostplant defense induction fungicides; (b48) multi-site contact activityfungicides; (b49) fungicides other than fungicides of classes (b1)through (b48); and salts of compounds of classes (b1) through (b48).

Further descriptions of these classes of fungicidal compounds areprovided below.

(b1) “Methyl benzimidazole carbamate (MBC) fungicides” (FRAC code 1)inhibit mitosis by binding to 1-tubulin during microtubule assembly.Inhibition of microtubule assembly can disrupt cell division, transportwithin the cell and cell structure. Methyl benzimidazole carbamatefungicides include benzimidazole and thiophanate fungicides. Thebenzimidazoles include benomyl, carbendazim, fuberidazole andthiabendazole. The thiophanates include thiophanate andthiophanate-methyl.

(b2) “Dicarboximide fungicides” (FRAC code 2) inhibit a MAP/histidinekinase in osmotic signal transduction. Examples include chlozolinate,iprodione, procymidone and vinclozolin.

(b3) “Demethylation inhibitor (DMI) fungicides” (FRAC code 3) (SterolBiosynthesis Inhibitors (SBI): Class I) inhibit C14-demethylase, whichplays a role in sterol production. Sterols, such as ergosterol, areneeded for membrane structure and function, making them essential forthe development of functional cell walls. Therefore, exposure to thesefungicides results in abnormal growth and eventually death of sensitivefungi. DMI fungicides are divided between several chemical classes:azoles (including triazoles and imidazoles), pyrimidines, piperazines,pyridines and triazolinthiones. The triazoles include azaconazole,bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole(including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole,ipconazole, metconazole, myclobutanil, penconazole, propiconazole,quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon,triadimenol, triticonazole, uniconazole, uniconazole-P,α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol,rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole,rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,andrel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole.The imidazoles include econazole, imazalil, oxpoconazole, prochloraz,pefurazoate and triflumizole. The pyrimidines include fenarimol,nuarimol and triarimol. The piperazines include triforine. The pyridinesinclude buthiobate, pyrifenox, pyrisoxazole(3-[(3R)-5-(4-chlorophenyl)-2,3-dimethyl3-isoxazolidinyl]pyridine,mixture of 3R,5R- and 3R,5S-isomers) and(aS)-[3-(4-chloro-2-fluorophenyl)5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol.The triazolinthiones include prothioconazole and2-[2-(1-chlorocyclopropyl)-4-(2,2-dichloro-cyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione.Biochemical investigations have shown that all of the above mentionedfungicides are DMI fungicides as described by K. H. Kuck et al. inModern Selective Fungicides-Properties, Applications and Mechanisms ofAction, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

(b4) “Phenylamide fungicides” (FRAC code 4) are specific inhibitors ofRNA polymerase in Oomycete fungi. Sensitive fungi exposed to thesefungicides show a reduced capacity to incorporate uridine into rRNA.Growth and development in sensitive fungi is prevented by exposure tothis class of fungicide. Phenylamide fungicides include acylalanine,oxazolidinone and butyrolactone fungicides. The acylalanines includebenalaxyl, benalaxyl-M (also known as kiralaxyl), furalaxyl, metalaxyland metalaxyl-M (also known as mefenoxam). The oxazolidinones includeoxadixyl. The butyrolactones include ofurace.

(b5) “Amine/morpholine fungicides” (FRAC code 5) (SBI: Class II) inhibittwo target sites within the sterol biosynthetic pathway, Δ⁸→Δ⁷ isomeraseand Δ¹⁴ reductase. Sterols, such as ergosterol, are needed for membranestructure and function, making them essential for the development offunctional cell walls. Therefore, exposure to these fungicides resultsin abnormal growth and eventually death of sensitive fungi.Amine/morpholine fungicides (also known as non-DMI sterol biosynthesisinhibitors) include morpholine, piperidine and spiroketal-aminefungicides. The morpholines include aldimorph, dodemorph, fenpropimorph,tridemorph and trimorphamide. The piperidines include fenpropidin andpiperalin. The spiroketal-amines include spiroxamine.

(b6) “Phospholipid biosynthesis inhibitor fungicides” (FRAC code 6)inhibit growth of fungi by affecting phospholipid biosynthesis.Phospholipid biosynthesis fungicides include phophorothiolate anddithiolane fungicides. The phosphorothiolates include edifenphos,iprobenfos and pyrazophos. The dithiolanes include isoprothiolane.

(b7) “Succinate dehydrogenase inhibitor (SDHI) fungicides” “(FRAC code7) inhibit Complex II fungal respiration by disrupting a key enzyme inthe Krebs Cycle (TCA cycle) named succinate dehydrogenase. Inhibitingrespiration prevents the fungus from making ATP, and thus inhibitsgrowth and reproduction. SDHI fungicides include phenylbenzamide, furancarboxamide, oxathiin carboxamide, thiazole carboxamide,pyrazole-4-carboxamide, pyridine carboxamide, phenyl oxoethyl thiopheneamides and pyridinylethyl benzamides. The benzamides include benodanil,flutolanil and mepronil. The furan carboxamides include fenfuram. Theoxathiin carboxamides include carboxin and oxycarboxin. The thiazolecarboxamides include thifluzamide. The pyrazole-4-carboxamides includebenzovindiflupyr(N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide),bixafen, fluxapyroxad(3-(difluoromethyl)-1-methyl-N-(3′,4′,5′-trifluoro[1,1′-biphenyl]-2-yl)-1H-pyrazole-4-carboxamide),furametpyr, isopyrazam(3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro9-(1-methylethyl)-1,4-methanonaphthalen-5-yl]-1H-pyrazole-4-carboxamnide),penflufen(N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide),penthiopyrad, sedaxane(N-[2-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide),N-[2-(1S,2R)-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide,N-[2-(2,4-dichlorophenyl)2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamideandN-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methyl-ethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide.The pyridine carboxamides include boscalid. The phenyl oxoethylthiophene amides include isofetamid(N-[1,1-dimethyl-2-[2-methyl-4-(1-methylethoxy)phenyl]-2-oxoethyl]-3-methyl-2-thiophenecarboxamide).The pyridinylethyl benzamides include fluopyram.

(b8) “Hydroxy-(2-amino-)pyrimidine fungicides” (FRAC code 8) inhibitnucleic acid synthesis by interfering with adenosine deaminase. Examplesinclude bupirimate, dimethirimol and ethirimol.

(b9) “Anilinopyrimidine fungicides” (FRAC code 9) are proposed toinhibit biosynthesis of the amino acid methionine and to disrupt thesecretion of hydrolytic enzymes that lyse plant cells during infection.Examples include cyprodinil, mepanipyrim and pyrimethanil.

(b10) “N-Phenyl carbamate fungicides” (FRAC code 10) inhibit mitosis bybinding to β-tubulin and disrupting microtubule assembly. Inhibition ofmicrotubule assembly can disrupt cell division, transport within thecell and cell structure. Examples include diethofencarb.

(b1) “Quinone outside inhibitor (QoI) fungicides” (FRAC code 11) inhibitComplex III mitochondrial respiration in fungi by affecting ubiquinoloxidase. Oxidation of ubiquinol is blocked at the “quinone outside”(Q_(o)) site of the cytochrome bc₁ complex, which is located in theinner mitochondrial membrane of fungi. Inhibiting mitochondrialrespiration prevents normal fungal growth and development. Quinoneoutside inhibitor fungicides include methoxyacrylate, methoxycarbamate,oximinoacetate, oximinoacetamide and dihydrodioxazine fungicides(collectively also known as strobilurin fungicides), andoxazolidinedione, imidazolinone and benzylcarbamate fungicides. Themethoxyacrylates include azoxystrobin, coumoxystrobin (methyl(αE)-2-[[(3-butyl-4-methyl-2-oxo-2H-1-benzopyran-7-yl)oxy]methyl]-α-(methoxymethylene)benzeneacetate),enoxastrobin (methyl(αE)-2-[[[(E)-[(2E)-3-(4-chlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]-α-(methoxymethylene)benzeneaceate)(also known as enestroburin), flufenoxystrobin (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate),picoxystrobin, and pyraoxystrobin (methyl(αE)-2-[[[3-(4-chlorophenyl)-1-methyl-1H-pyrazol-5-yl]oxy]methyl]-α-(methoxymethylene)benzeneacetate).The methoxy-carbamates include pyraclostrobin, pyrametostrobin (methylN-[2-[[(1,4-dimethyl-3-phenyl-1H-pyrazol-5-yl)oxy]methyl]phenyl]-N-methoxycarbamate)and triclopyricarb (methylN-methoxy-N-[2-[[(3,5,6-trichloro-2-pyridinyl)oxy]methyl]phenyl]carbamate).The oximino-acetates include kresoxim-methyl, and trifloxystrobin. Theoximinoacetamides include dimoxystrobin, fenaminstrobin((αE)-2-[[[(E)-[(2E)-3-(2,6-dichlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]-α-(methoxyimino)-N-methylbenzeneacetamide),metominostrobin, orysastrobin andα-[methoxyimino]-N-methyl-2-[[[1-[3-(trifluoro-methyl)phenyl]ethoxy]imino]methyl]benzeneacetamide.The dihydrodioxazines include fluoxastrobin. The oxazolidinedionesinclude famoxadone. The imidazolinones include fenamidone. Thebenzylcarbamates include pyribencarb. Class (b11) also includesmandestrobin(2-[(2,5-dimethylphenoxy)methyl]-α-methoxy-N-benzeneacetamide).

(b12) “Phenylpyrrole fungicides” (FRAC code 12) inhibit a MAP/histidinekinase associated with osmotic signal transduction in fungi. Fenpicloniland fludioxonil are examples of this fungicide class.

(b13) “Azanaphthalene fungicides” (FRAC code 13) are proposed to inhibitsignal transduction by a mechanism which is as yet unknown. They havebeen shown to interfere with germination and/or appressorium formationin fungi that cause powdery mildew diseases. Azanaphthalene fungicidesinclude aryloxyquinolines and quinazolinones. The aryloxyquinolinesinclude quinoxyfen. The quinazolinones include proquinazid.

(b14) “Lipid peroxidation inhibitor fungicides” (FRAC code 14) areproposed to inhibit lipid peroxidation which affects membrane synthesisin fungi. Members of this class, such as etridiazole, may also affectother biological processes such as respiration and melanin biosynthesis.Lipid peroxidation fungicides include aromatic hydrocarbon and1,2,4-thiadiazole fungicides. The aromatic hydrocarboncarbon fungicidesinclude biphenyl, chloroneb, dicloran, quintozene, tecnazene andtolclofos-methyl. The 1,2,4-thiadiazoles include etridiazole.

(b15) “Melanin biosynthesis inhibitors-reductase (MBI-R) fungicides”(FRAC code 16.1) inhibit the naphthal reduction step in melaninbiosynthesis. Melanin is required for host plant infection by somefungi. Melanin biosynthesis inhibitors-reductase fungicides includeisobenzofuranone, pyrroloquinolinone and triazolobenzothiazolefungicides. The isobenzofuranones include fthalide. Thepyrroloquinolinones include pyroquilon. The triazolobenzothiazolesinclude tricyclazole.

(b16) “Melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides”(FRAC code 16.2) inhibit scytalone dehydratase in melanin biosynthesis.Melanin in required for host plant infection by some fungi. Melaninbiosynthesis inhibitors-dehydratase fungicides includecyclopropanecarboxamide, carboxamide and propionamide fungicides. Thecyclopropanecarboxamides include carpropamid. The carboxamides includediclocymet. The propionamides include fenoxanil.

(b17) “Sterol Biosynthesis Inhibitor (SBI): Class III fungicides (FRACcode 17) inhibit 3-ketoreductase during C4-demethylation in sterolproduction. SBI: Class III inhibitors include hydroxyanilide fungicidesand amino-pyrazolinone fungicides. Hydroxyanilides include fenhexamid.Amino-pyrazolinones include fenpyrazamine (S-2-propen-1-yl5-amino-2,3-dihydro-2-(1-methylethyl)-4-(2-methylphenyl)-3-oxo-1H-pyrazole-1-carbothioate).

(b18) “Squalene-epoxidase inhibitor fungicides” (FRAC code 18) (SBI:Class IV) inhibit squalene-epoxidase in the sterol biosynthesis pathway.Sterols such as ergosterol are needed for membrane structure andfunction, making them essential for the development of functional cellwalls. Therefore, exposure to these fungicides results in abnormalgrowth and eventually death of sensitive fungi. Squalene-epoxidaseinhibitor fungicides include thiocarbamate and allylamine fungicides.The thiocarbamates include pyributicarb. The allylamines includenaftifine and terbinafine.

(b19) “Polyoxin fungicides” (FRAC code 19) inhibit chitin synthase.Examples include polyoxin.

(b20) “Phenylurea fungicides” (FRAC code 20) are proposed to affect celldivision. Examples include pencycuron.

(b21) “Quinone inside inhibitor (QiI) fungicides” (FRAC code 21) inhibitComplex III mitochondrial respiration in fungi by affecting ubiquinonereductase. Reduction of ubiquinone is blocked at the “quinone inside”(Qi) site of the cytochrome bc₁ complex, which is located in the innermitochondrial membrane of fungi. Inhibiting mitochondrial respirationprevents normal fungal growth and development. Quinone inside inhibitorfungicides include cyanoimidazole and sulfamoyltriazole fungicides. Thecyanoimidazoles include cyazofamid. The sulfamoyltriazoles includeamisulbrom.

(b22) “Benzamide and thiazole carboxamide fungicides” (FRAC code 22)inhibit mitosis by binding to β-tubulin and disrupting microtubuleassembly. Inhibition of microtubule assembly can disrupt cell division,transport within the cell and cell structure. The benzamides includezoxamide. The thiazole carboxamides include ethaboxam.

(b23) “Enopyranuronic acid antibiotic fungicides” (FRAC code 23) inhibitgrowth of fungi by affecting protein biosynthesis. Examples includeblasticidin-S.

(b24) “Hexopyranosyl antibiotic fungicides” (FRAC code 24) inhibitgrowth of fungi by affecting protein biosynthesis. Examples includekasugamycin.

(b25) “Glucopyranosyl antibiotic: protein synthesis fungicides” (FRACcode 25) inhibit growth of fungi by affecting protein biosynthesis.Examples include streptomycin.

(b26) “Glucopyranosyl antibiotic: trehalase and inositol biosynthesisfungicides” (FRAC code 26) inhibit trehalase and inositol biosynthesis.Examples include validamycin.

(b27) “Cyanoacetamideoxime fungicides (FRAC code 27) include cymoxanil.

(b28) “Carbamate fungicides” (FRAC code 28) are considered multi-siteinhibitors of fungal growth. They are proposed to interfere with thesynthesis of fatty acids in cell membranes, which then disrupts cellmembrane permeability. Propamacarb, iodocarb, and prothiocarb areexamples of this fungicide class.

(b29) “Oxidative phosphorylation uncoupling fungicides” (FRAC code 29)inhibit fungal respiration by uncoupling oxidative phosphorylation.Inhibiting respiration prevents normal fungal growth and development.This class includes 2,6-dinitroanilines such as fluazinam, anddinitrophenyl crotonates such as dinocap, meptyldinocap and binapacryl.

(b30) “Organo tin fungicides” (FRAC code 30) inhibit adenosinetriphosphate (ATP) synthase in oxidative phosphorylation pathway.Examples include fentin acetate, fentin chloride and fentin hydroxide.

(b31) “Carboxylic acid fungicides” (FRAC code 31) inhibit growth offungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II(gyrase). Examples include oxolinic acid.

(b32) “Heteroaromatic fungicides” (Fungicide Resistance Action Committee(FRAC) code 32) are proposed to affect DNA/ribonucleic acid (RNA)synthesis. Heteroaromatic fungicides include isoxazoles andisothiazolones. The isoxazoles include hymexazole and the isothiazolonesinclude octhilinone.

(b33) “Phosphonate fungicides” (FRAC code 33) include phosphorous acidand its various salts, including fosetyl-aluminum.

(b34) “Phthalamic acid fungicides” (FRAC code 34) include teclofthalam.

(b35) “Benzotriazine fungicides” (FRAC code 35) include triazoxide.

(b36) “Benzene-sulfonamide fungicides” (FRAC code 36) includeflusulfamide.

(b37) “Pyridazinone fungicides” (FRAC code 37) include diclomezine.

(b38) “Thiophene-carboxamide fungicides” (FRAC code 38) are proposed toaffect ATP production. Examples include silthiofam.

(b39) “Complex I NADH oxidoreductase inhibitor fungicides” (FRAC code39) inhibit electron transport in mitochondria and includepyrimidinamines such as diflumetorim, and pyrazole-5-carboxamides suchas tolfenpyrad.

(b40) “Carboxylic acid amide (CAA) fungicides” (FRAC code 40) inhibitcellulose synthase which prevents growth and leads to death of thetarget fungus. Carboxylic acid amide fungicides include cinnamic acidamide, valinamide and other carbamate, and mandelic acid amidefungicides. The cinnamic acid amides include dimethomorph, flumorph andpyrimorph(3-(2-chloro-4-pyridinyl)-3-[4-(1,1-dimethylethyl)phenyl]-1-(4-morpholinyl)-2-propene-1-one).The valinamide and other carbamates include benthiavalicarb,benthiavalicarb-isopropyl, iprovalicarb, tolprocarb(2,2,2-trifluoroethylN-[(1S)-2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamate) andvalifenalate (methylN-[(1-methylethoxy)carbonyl]-L-valyl-3-(4-chlorophenyl)-3-alaninate)(also known as valiphenal). The mandelic acid amides includemandipropamid,N-[2-[4-[[3-(4-chloro-phenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)amino]-butanamideandN-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.

(b41) “Tetracycline antibiotic fungicides” (FRAC code 41) inhibit growthof fungi by affecting protein synthesis. Examples includeoxytetracycline.

(b42) “Thiocarbamate fungicides” (FRAC code 42) include methasulfocarb.

(b43) “Benzamide fungicides” (FRAC code 43) inhibit growth of fungi bydelocalization of spectrin-like proteins. Examples includepyridinylmethyl benzamide fungicides such as fluopicolide (now FRAC code7, pyridinylethyl benzamides).

(b44) “Microbial fungicides” (FRAC code 44) disrupt fungal pathogen cellmembranes. Microbial fungicides include Bacillus species such asBacillus amyloliquefaciens strains QST 713, FZB24, MB1600, D747 and thefungicidal lipopeptides which they produce.

(b45) “Q_(X)I fungicides” (FRAC code 45) inhibit Complex IIImitochondrial respiration in fungi by affecting ubiquinone reductase atan unknown (Q_(x)) site of the cytochrome bcl complex. Inhibitingmitochondrial respiration prevents normal fungal growth and development.Q_(X)I fungicides include triazolopyrimidylamines such as ametoctradin(5-ethyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidin-7-amine).

(b46) “Plant extract fungicides” are proposed to act by cell membranedisruption. Plant extract fungicides include terpene hydrocarbons andterpene alcohols such as the extract from Melaleuca alternifolia (teatree).

(b47) “Host plant defense induction fungicides” (FRAC code P) inducehost plant defense mechanisms. Host plant defense induction fungicidesinclude benzothiadiazoles, benzisothiazole and thiadiazole-carboxamidefungicides. The benzothiadiazoles include acibenzolar-S-methyl. Thebenzisothiazoles include probenazole. The thiadiazole-carboxamidesinclude tiadinil and isotianil.

(b48) “Multi-site contact fungicides” inhibit fungal growth throughmultiple sites of action and have contact/preventive activity. Thisclass of fungicides includes: (b48.1) “copper fungicides” (FRAC codeM1)”, (b48.2) “sulfur fungicides” (FRAC code M2), (b48.3)“dithiocarbamate fungicides” (FRAC code M3), (b48.4) “phthalimidefungicides” (FRAC code M4), (b48.5) “chloronitrile fungicides” (FRACcode M5), (b48.6) “sulfamide fungicides” (FRAC code M6), (b48.7)multi-site contact “guanidine fungicides” (FRAC code M7), (b48.8)“triazine fungicides” (FRAC code M8), (b48.9) “quinone fungicides” (FRACcode M9), (b48.10) “quinoxaline fungicides” (FRAC code M10) and (b48.11)“maleimide fungicides” (FRAC code M11). “Copper fungicides” areinorganic compounds containing copper, typically in the copper(II)oxidation state; examples include copper oxychloride, copper sulfate andcopper hydroxide, including compositions such as Bordeaux mixture(tribasic copper sulfate). “Sulfur fungicides” are inorganic chemicalscontaining rings or chains of sulfur atoms; examples include elementalsulfur. “Dithiocarbamate fungicides” contain a dithiocarbamate molecularmoiety; examples include mancozeb, metiram, propineb, ferbam, maneb,thiram, zineb and ziram. “Phthalimide fungicides” contain a phthalimidemolecular moiety; examples include folpet, captan and captafol.“Chloronitrile fungicides” contain an aromatic ring substituted withchloro and cyano; examples include chlorothalonil. “Sulfamidefungicides” include dichlofluanid and tolyfluanid. Multi-site contact“guanidine fungicides” include, guazatine, iminoctadine albesilate andiminoctadine triacetate. “Triazine fungicides” include anilazine.“Quinone fungicides” include dithianon. “Quinoxaline fungicides” includequinomethionate (also known as chinomethionate). “Maleimide fungicides”include fluoroimide.

(b49) “Fungicides other than fungicides of classes (b1) through (b48)”include certain fungicides whose mode of action may be unknown. Theseinclude: (b49.1), “phenyl-acetamide fungicides” (FRAC code U6), (b49.2)“aryl-phenyl-ketone fungicides” (FRAC code U8), (b49.3) “guanidinefungicides” (FRAC code U12), (b49.4) “thiazolidine fungicides” (FRACcode U13), (b49.5) “pyrimidinone-hydrazone fungicides” (FRAC code U14)and (b49.6) compounds that bind to oxysterol-binding protein asdescribed in PCT Patent Publication WO 2013/009971. Thephenyl-acetamides include cyflufenamid andN-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]-benzeneacetamide.The aryl-phenyl ketones include benzophenones such as metrafenone, andbenzoylpyridines such as pyriofenone(5-chloro-2-methoxy-4-methyl-3-pyridinyl)(2,3,4-trimethoxy-6-methylphenyl)methanone).The quanidines include dodine. The thiazolidines include flutianil((2Z)-2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile).The pyrimidinonehydrazones include ferimzone. The (b49.6) class includesoxathiapiprolin(1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone)and its R-enantiomer which is1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]-ethanone(Registry Number 1003319-79-6). The (b49) class also includesbethoxazin, flometoquin(2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinylmethyl carbonate), fluoroimide, neo-asozin (ferric methanearsonate),picarbutrazox (1,1-dimethylethylN-[6-[[[[((Z)1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate),pyrrolnitrin, quinomethionate, tebufloquin(6-(1,1-dimethylethyl)-8-fluoro-2,3-dimethyl-4-quinolinyl acetate),tolnifanide(N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide),2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-butyn-1-ylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]-carbamate,(N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide),N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]benzeneacetamide,2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone,5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine,5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine and 4-fluorophenylN-[1-[[[1-(4-cyano-phenyl)ethyl]sulfonyl]methyl]propyl]carbamate, pentylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate,pentylN-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamateand pentylN-[6-[[[[(Z)-(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]-carbamate.The (b46) class further includes mitosis- and cell division-inhibitingfungicides besides those of the particular classes described above(e.g., (b1), (b10) and (b22)).

Additional “Fungicides other than fungicides of classes (1) through(46)” whose mode of action may be unknown, or may not yet be classifiedinclude a fungicidal compound selected from components (b49.7) through(b49.12), as shown below.

Component (b49.7) relates to a compound of Formula b49.7

-   -   wherein R^(b1) is —OCH₂ or        Examples of a compound of Formula b49.7 include (b49.7a)        (2-chloro-6-fluorophenyl)-methyl        2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate        (Registry Number 1299409-40-7) and (b49.7b)        (1R)-1,2,3,4-tetrahydro-1-naphthalenyl        2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate        (Registry Number 1299409-42-9). Methods for preparing compounds        of Formula b46.2 are described in PCT Patent Publications WO        2009/132785 and WO 2011/051243.

Component (b49.8) relates to a compound of Formula b49.8

-   -   wherein R^(b2) is CH₃, CF₃ or CHF₂; R^(b3) is CH₃, CF₃ or CHF₂;        R^(b4) is halogen or cyano; and n is 0, 1, 2 or 3.        Examples of a compound of Formula b49.8 include (b49.8a)        1-[4-[4-[5-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperdinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone.        Methods for preparing compounds of Formula b49.8 are described        in PCT Patent Application PCT/US11/64324.

Component (b4799) relates to a compound of Formula b49.9

-   -   wherein R^(b5) is —CH₂OC(O)CH(CH₃)₂, —C(O)CH₃, —CH₂OC(O)CH₃,        —C(O)OCH₂CH(CH₃)₂ or

Examples of a compound of Formula b49.9 include (b49.9a)[[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]methyl2-methylpropanoate (also known as fenpicoxamid) (Registry Number517875-34-2), (b49.9b)(3S,6S,7R,8R)-3-[[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate (Registry Number 234112-93-7), (b49.9c)(3S,6S,7R,8R)-3[[[3[(acetyloxy)methoxy]-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate (Registry Number 517875-31-9), (b49.9d)(3S,6S,7R,8R)-3-[[[4-methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridinyl]-carbonyl]amino]6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate (Registry Number 328256-72-0), and(b49.9e)N-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-2-pyridinyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxopropyl)-2-(phenylmethyl)L-arabinonoyl]-L-serine,(1→4′)-lactone (Registry Number 1285706-70-8). Methods for preparingcompounds of Formula b49.9 are described in PCT Patent Publications WO99/40081, WO 2001/014339, WO 2003/035617 and WO 2011044213.

Component (b49.10) relates to a compound of Formula b49.10

wherein R^(b6) is H or F, and R^(b7) is —CF₂CHFCF₃ or —CF₂CF₂H. Examplesof a compound of Formula b49.10 are (b49.10a)3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoro-propoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide(Registry Number 1172611-40-3) and (b49.10b)3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole4-carboxamide(Registry Number 923953-98-4). Compounds of Formula 49.10 can beprepared by methods described in PCT Patent Publication WO 2007/017450.

Component b49.11 relates a compound of Formula b49.11

wherein

-   -   R^(b8) is halogen, C₁-C₄ alkoxy or C₂-C₄ alkynyl;    -   R^(b9) is H, halogen or C₁-C₄ alkyl;    -   R^(b10) is C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₂-C₁₂        alkoxyalkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₄-C₁₂        alkoxyalkenyl, C₄-C₁₂ alkoxyalkynyl, C₁-C₁₂ alkylthio or C₂-C₁₂        alkylthioalkyl;    -   R^(b11) is methyl or —Y^(b13)—R^(b12);    -   R^(b12) is C₁-C₂ alkyl; and    -   Y^(b13) is CH₂, O or S.

Examples of compounds of Formula b49.11 include (b49.11a)2-[(3-bromo-6-quinolinyl)-oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide,(b49.11b)2[(3-ethynyl-6-quinolinyl)oxy]-N-[1-(hydroxymethyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)acetamide,(b49.11c)N-(1,1-dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)-acetamide,(b49.11d)2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-propyn-1-yl)-2-(methylthio)acetamideand (b49.11e)2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-di-methylethyl)butanamide.Compounds of Formula b49.11, their use as fungicides and methods ofpreparation are generally known; see, for example, PCT PatentPublications WO 2004/047538, WO 2004/108663, WO 2006/058699, WO2006/058700, WO 2008/110355, WO 2009/030469, WO 2009/049716 and WO2009/087098.

Component 49.12 relates toN-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,which is believed to inhibit C24-methyl transferase involved in thebiosynthesis of sterols.

Therefore of note is a mixture (i.e. composition) comprising a compoundof Formula 1 and at least one fungicidal compound selected from thegroup consisting of the aforedescribed classes (1) through (49). Also ofnote is a composition comprising said mixture (in fungicidally effectiveamount) and further comprising at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents. Of particular note is a mixture (i.e. composition)comprising a compound of Formula 1 and at least one fungicidal compoundselected from the group of specific compounds listed above in connectionwith classes (1) through (49). Also of particular note is a compositioncomprising said mixture (in fungicidally effective amount) and furthercomprising at least one additional surfactant selected from the groupconsisting of surfactants, solid diluents and liquid diluents.

Examples of component (b) fungicides include acibenzolar-S-methyl,aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole,azoxystrobin, benalaxyl (including benalaxyl-M), benodanil, benomyl,benthiavalicarb (including benthiavalicarb-isopropyl), benzovindiflupyr,bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S,boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan,carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil,chlozolinate, clotrimazole, copper hydroxide, copper oxychloride, coppersulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil,cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine,dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol,dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M),dinocap, dithianon, dithiolanes, dodemorph, dodine, econazole,edifenphos, enoxastrobin (also known as enestroburin), epoxiconazole,etaconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone,fenarimol, fenaminstrobin, fenbuconazole, fenfuram, fenhexamid,fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine,fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone,flometoquin, fluazinam, fludioxonil, flufenoxystrobin, flumorph,fluopicolide, fluopyram, flouroimide, fluoxastrobin, fluquinconazole,flusilazole, flusulfamide, flutianil, flutolanil, flutriafol,fluxapyroxad, folpet, fthalide, fuberidazole, furalaxyl, furametpyr,guazatine, hexaconazole, hymexazole, imazalil, imibenconazole,iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole,iprobenfos, iprodione, iprovalicarb, isoconazole, isofetamid,isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl,mancozeb, mandepropamid, mandestrobin, maneb, mepanipyrim, mepronil,meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), metconazole,methasulfocarb, metiram, metominostrobin, metrafenone, miconazole,myclobutanil, naftifine, neo-asozin, nuarimol, octhilinone, ofurace,orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid, oxpoconazole,oxycarboxin, oxytetracycline, pefurazoate, penconazole, pencycuron,penflufen, penthiopyrad, phosphorous acid (including salts thereof,e.g., fosetyl-aluminum), picarbutrazox, picoxystrobin, piperalin,polyoxin, probenazole, prochloraz, procymidone, propamacarb,propiconazole, propineb, proquinazid, prothiocarb, prothioconazole,pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos,pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone,pyrisoxazole, pyroquilon, pyrrolnitrin, quinconazole, quinomethionate,quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, spiroxamine,streptomycin, sulfur, tebuconazole, tebufloquin, teclofthalam,tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide,thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl,tolnifanide, tolprocarb, tolyfluanid, triadimefon, triadimenol,triarimol, triticonazole, triazoxide, tribasic copper sulfate,tricyclazole, triclopyricarb, tridemorph, trifloxystrobin, triflumizole,triforine, trimorphamide, uniconazole, uniconazole-P, validamycin,valifenalate (also known as valiphenal), vinclozolin, zineb, ziram,zoxamide,(3S,6S,7R,8R)-3-[[[3-[(acetyloxy)methoxy]-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate,(3S,6S,7R,8R)-3-[[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate,N-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-2-pyridinyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxopropyl)-2-(phenylmethyl)-L-arabinonoyl]-L-serine,(1→4′)-lactone,N-[2-(1S,2R)-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide,2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethylethyl)butanamide,2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-propyn-1-yl)-2-(methylthio)acetamide,2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-butyn-1-ylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]-amino]oxy]methyl]-2-pyridinyl]carbamate,α-(1-chlorocyclopopropyl)-α-[2-(2,2dichloro-cyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol,2-[2-(1-chlorocyclopropyl)-4-(2,2-dichloro-cyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,(αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol,rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole,rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole,3-[5-(4-chlorophenyl)-2,3-di-methyl-3-isoxazolidinyl]pyridine,(2-chloro-6-fluorophenyl)methyl2-[1-[2-[3,5-bis(di-fluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate,N′-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]-ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide,N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methyl-ethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide,N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide,N-[2-(2,4-dichloro-phenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,N-(3′,4′-difluoro[1,1′-biphenyl]-2-yl)-3-(trifluoromethyl)-2-pyrazinecarboxamide,3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide,3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoropropoxy)-phenyl]-1-methyl-1H-pyrazole-4-carboxamide,5,8-difluoro-N-[2-[3-methoxy-4-[[4-(trifluoromethyl)-2-pyridinyl]oxy]phenyl]ethyl]-4-quinazolinamine,3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide,1-[4-[4-[5R-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperdinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone,N-(1,1-dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)acetamide,2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone,2-[(3-ethynyl-6-quinolinyl)oxy]-N-[1-(hydroxy-methyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)acetamide,4-fluorophenylN-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate,5-fluoro-2-[(4-fluorophenyl)-methoxy]-4-pyrimidinamine,5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine,(3S,6S,7R,8R)-3-[[[4-methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridinyl]-carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl-2-methylpropanoate,α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]imino]-methyl]benzeneacetamide,[[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxo-propoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]methyl2-methylpropanoate, pentylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)-phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate,pentylN-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamate,and pentylN-[6-[[[[(Z)-(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]-carbamateand (1R)-1,2,3,4-tetrahydro-1-naphthalenyl2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate.Therefore of note is a fungicidal composition comprising as component(a) a compound of Formula 1 (or an N-oxide or salt thereof) and ascomponent (b) at least one fungicide selected from the preceding list.

Of particular note are combinations of compounds of Formula 1 (or anN-oxide or salt thereof) (i.e. Component (a) in compositions) withazoxystrobin, benzovindiflupyr, bixafen, captan, carpropamid,chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate,cymoxanil, cyproconazole, cyprodinil, diethofencarb, difenoconazole,dimethomorph, epoxiconazole, ethaboxam, fenarimol, fenhexamid,fluazinam, fludioxonil, fluopyram, flusilazole, flutianil, flutriafol,fluxapyroxad, folpet, iprodione, isofetamid, isopyrazam,kresoxim-methyl, mancozeb, mandestrobin, meptyldinocap, metalaxyl(including metalaxyl-M/mefenoxam), metconazole, metrafenone,myclobutanil, oxathiapiprolin, penflufen, penthiopyrad, phosphorous acid(including salts thereof, e.g., fosetyl-aluminum), picoxystrobin,propiconazole, proquinazid, prothioconazole, pyraclostrobin,pyrimethanil, sedaxane spiroxamine, sulfur, tebuconazole,thiophanate-methyl, trifloxystrobin, zoxamide,α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol,2-[2-(1chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoro-methyl)-1-methyl-1H-pyrazole-4-carboxamide,3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide,1-[4-[4-[5R-(2,6-difluoro-phenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone,1,1-dimethylethylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate,2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone,5-fluoro-2-[(4-fluoro-phenyl)methoxy]-4-pyrimidinamine,5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine,(aS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol,rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole,rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]-methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,andrel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole(i.e. as Component (b) in compositions).

Examples of other biologically active compounds or agents with whichcompounds of this invention can be formulated are: invertebrate pestcontrol compounds or agents such as abamectin, acephate, acetamiprid,acrinathrin, afidopyropen ([(3S,4R,4aR,6S,6aS,12R, 12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxy-late), amidoflumet (S-1955), avermectin,azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin,carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorfluazuron,chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin,cyantraniliprole(3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide),cyclaniliprole (3-bromo-N-[2-bromo-4-chloro-6-[[(1-cyclopropyl-ethyl)amino]carbonyl]phenyl]1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide),cycloxaprid((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-epoxy-1H-imidazo[1,2-a]azepine),cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin,diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin,dimethoate, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin,fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate,flufenoxystrobin (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate),flufensulfone(5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole),flupiprole(1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoro-methyl)sulfinyl]-1H-pyrazole-3-carbonitrile),flupyradifurone(4-[[(6-chloro-3-pyridinyl)-methyl](2,2-difluoroethyl)amino]-2(5H)-furanone),tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonophos,halofenozide, heptafluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclo-propanecarboxylate),hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos,lufenuron, malathion, meperfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl(1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate),metaflumizone, metaldehyde, methamidophos, methidathion, methomyl,methoprene, methoxychlor, methoxyfenozide, metofluthrin, milbemycinoxime, momfluorothrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl-3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate),monocrotophos, nicotine, nitenpyram, nithiazine, novaluron, noviflumuron(XDE-007), oxamyl, pyflubumide(1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide),parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet,phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine,pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon, pyriminostrobin(methyl(αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxy-methylene)benzeneacetate),pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad,spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulfoxaflor,sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos,tetrachlorvinphos, tetramethylfluthrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon and triflumuron; and biological agents includingentomopathogenic bacteria, such as Bacillus thuringiensis subsp.aizawai, Bacillus thuringiensis subsp. kurstaki, and the encapsulateddelta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII);entomopathogenic fungi, such as green muscardine fungus; andentomopathogenic virus including baculovirus, nucleopolyhedro virus(NPV) such as HzNPV, AfNPV; and granulosis virus (GV) such as CpGV.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). The effect ofthe exogenously applied fungicidal compounds of this invention may besynergistic with the expressed toxin proteins.

General references for agricultural protectants (i.e. insecticides,fungicides, nematocides, acaricides, herbicides and biological agents)include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed.,British Crop Protection Council, Farnham, Surrey, U. K., 2003 and TheBioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British CropProtection Council, Farnham, Surrey, U. K., 2001.

For embodiments where one or more of these various mixing partners areused, the weight ratio of these various mixing partners (in total) tothe compound of Formula 1 is typically between about 1:3000 and about3000:1. Of note are weight ratios between about 1:300 and about 300:1(for example ratios between about 1:30 and about 30:1). One skilled inthe art can easily determine through simple experimentation thebiologically effective amounts of active ingredients necessary for thedesired spectrum of biological activity. It will be evident thatincluding these additional components may expand the spectrum ofdiseases controlled beyond the spectrum controlled by the compound ofFormula 1 alone.

In certain instances, combinations of a compound of this invention withother biologically active (particularly fungicidal) compounds or agents(i.e. active ingredients) can result in a greater-than-additive (i.e.synergistic) effect. Reducing the quantity of active ingredientsreleased in the environment while ensuring effective pest control isalways desirable. When synergism of fungicidal active ingredients occursat application rates giving agronomically satisfactory levels of fungalcontrol, such combinations can be advantageous for reducing cropproduction cost and decreasing environmental load.

Also in certain instances, combinations of a compound of the inventionwith other biologically active compounds or agents can result in aless-than-additive (i.e. safening) effect on organisms beneficial to theagronomic environment. For example, a compound of the invention maysafen a herbicide on crop plants or protect a beneficial insect species(e.g., insect predators, pollinators such as bees) from an insecticide.

Fungicides of note for formulation with compounds of Formula 1 toprovide mixtures useful in seed treatment include but are not limited toamisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil,cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil,flufenoxystrobin, fluquinconazole, fluopicolide, fluoxastrobin,flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam,metconazole, myclobutanil, paclobutrazole, penflufen, picoxystrobin,prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole,thiabendazole, thiophanate-methyl, thiram, trifloxystrobin andtriticonazole.

Invertebrate pest control compounds or agents with which compounds ofFormula 1 can be formulated to provide mixtures useful in seed treatmentinclude but are not limited to abamectin, acetamiprid, acrinathrin,afidopyropen, amitraz, avermectin, azadirachtin, bensultap, bifenthrin,buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin,cyantraniliprole, cyclaniliprole, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flonicamid, flubendiamide, fluensulfone, flufenoxuron,flufiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate,heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb,lufenuron, meperfluthrin, metaflumizone, methiocarb, methomyl,methoprene, methoxyfenozide, momfluorothrin, nitenpyram, nithiazine,novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin, pyridaben,pyriminostrobin, pyridalyl, pyriproxyfen, ryanodine, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor,tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid,thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate,triflumuron, Bacillus thuringiensis delta-endotoxins, strains ofBacillus thuringiensis and strains of Nucleo polyhydrosis viruses.

Compositions comprising compounds of Formula 1 useful for seed treatmentcan further comprise bacteria and fungi that have the ability to provideprotection from the harmful effects of plant pathogenic fungi orbacteria and/or soil born animals such as nematodes. Bacteria exhibitingnematicidal properties may include but are not limited to Bacillusfirmus, Bacillus cereus, Bacillius subtilis and Pasteuria penetrans. Asuitable Bacillus firmus strain is strain CNCM I-1582 (GB-126) which iscommercially available as BioNem™. A suitable Bacillus cereus strain isstrain NCMM 1-1592. Both Bacillus strains are disclosed in U.S. Pat. No.6,406,690. Other suitable bacteria exhibiting nematicidal activity areB. amyloliquefaciens IN937a and B. subtilis strain GB03. Bacteriaexhibiting fungicidal properties may include but are not limited to B.pumilus strain GB34. Fungal species exhibiting nematicidal propertiesmay include but are not limited to Myrothecium verrucaria, Paecilomyceslilacinus and Purpureocillium lilacinum.

Seed treatments can also include one or more nematicidal agents ofnatural origin such as the elicitor protein called harpin which isisolated from certain bacterial plant pathogens such as Erwiniaamylovora. An example is the Harpin-N-Tek seed treatment technologyavailable as N-Hibit™ Gold CST.

Seed treatments can also include one or more species of legume-rootnodulating bacteria such as the microsymbiotic nitrogen-fixing bacteriaBradyrhizobium japonicum. These inocculants can optionally include oneor more lipo-chitooligosaccharides (LCOs), which are nodulation (Nod)factors produced by rhizobia bacteria during the initiation of noduleformation on the roots of legumes. For example, the Optimize® brand seedtreatment technology incorporates LCO Promoter Technology™ incombination with an inocculant.

Seed treatments can also include one or more isoflavones which canincrease the level of root colonization by mycorrhizal fungi.Mycorrhizal fungi improve plant growth by enhancing the root uptake ofnutrients such as water, sulfates, nitrates, phosphates and metals.Examples of isoflavones include, but are not limited to, genistein,biochanin A, formononetin, daidzein, glycitein, hesperetin, naringeninand pratensein. Formononetin is available as an active ingredient inmycorrhizal inocculant products such as PHC Colonize® AG.

Seed treatments can also include one or more plant activators thatinduce systemic acquired resistance in plants following contact by apathogen. An example of a plant activator which induces such protectivemechanisms is acibenzolar-S-methyl.

The following TESTS demonstrate the control efficacy of compounds ofthis invention on specific pathogens. The pathogen control protectionafforded by the compounds is not limited, however, to these species. SeeIndex Tables A-G below for compound descriptions. The followingabbreviations are used in the Index Tables: Me means methyl, Et meansethyl, n-Pr means n-propyl, i-Pr means iso-propyl, c-Pr meanscyclopropyl, t-Bu means tert-butyl, Ph means phenyl, MeO means methoxyand EtO means ethoxy. The abbreviation “Cmpd. No.” stands for “CompoundNumber”, and the abbreviation “Ex.” stands for “Example” and is followedby a number indicating in which example the compound is prepared. ¹⁹FNMR spectra are reported in ppm relative to trichlorofluoromethane inCDCl₃ solution unless indicated otherwise. The numerical value reportedin the column “MS” is the molecular weight of the highest isotopicabundance positively charged parent ion (M+1) formed by addition of H⁺(molecular weight of 1) to the molecule having the highest isotopicabundance, or the highest isotopic abundance negatively charged ion(M−1) formed by loss of H+(molecular weight of 1). The presence ofmolecular ions containing one or more higher atomic weight isotopes oflower abundance (e.g., ³⁷Cl, ⁸¹Br) is not reported. The reported MSpeaks were observed by mass spectrometry using electrospray ionization(ESI) or atmospheric pressure chemical ionization (APCI).

INDEX TABLE A

A dash “—” in the R^(3c) column means that no R^(3c) substituent ispresent and the remaining carbon valences are occupied by hydrogenatoms. In the Z² column, the bond projecting to the left is attached toC═O, and the bond projecting to the right is attached to the phenylring. ¹⁹F MP Cmpd. R¹ Z¹ Z² R^(3c) NMR ° C. MS 1 Ph NH —OCH₂— — −65.42 2CH₃CH₂ NH —OCH₂— — −65.37  99-101 3 i-Pr NH —OCH₂— — −65.36 4EtOC(═O)CH₂ NH —OCH₂— — −65.36 5 CH₃CH₂ NH —OCH₂CH(OMe)— — −65.35 6 CH₃N(Me) —OCH₂— — −65.35 7 ClCH₂CH₂ NH —OCH₂— — −65.35 9 CH₃ NH —OCH₂— —−65.36 10 CH₃CH₂CH₂ NH —OCH₂— — −65.36 11 MeOCH₂CH₂ NH —OCH₂— — −65.3612 CH≡CCH₂ NH —OCH₂— — −65.35 94-96 13 PhCH₂ NH —OCH₂— — −65.35 14CH₃CH₂CH(Me) NH —OCH₂— — −65.36 15 n-Bu NH —OCH₂— — −65.36 16 t-Bu NH—OCH₂— — −65.37 17 (Ex. 4) H NH —OCH₂— — −65.35 142-144 19 CH₃CH₂ NH—OCH(Me)— — −65.44 20 CH₃CH₂ NH —OCH₂CH₂CH₂— — −65.36 344 (M + 1) 223-pyridinyl NH —OCH₂— — −65.33 365 (M + 1) 23 (Ex. 3) 3-pyridinyl NH—OCH(Me)— — −65.35 379 (M + 1) 24 4-(MeOC(═O))PhCH₂ NH —OCH₂— — −65.35436 (M + 1) 25 4-(MeOC(═O))PhCH₂ NH —OCH(Me)— — −65.35 450 (M + 1) 264-(EtOC(═O))PhCH₂ NH —OCH₂— — −65.39 450 (M + 1) 27 4-(EtOC(═O))PhCH₂ NH—OCH(Me)— — −65.35 464 (M + 1) 28 CH₃ N(Me) —OCH₂CH₂CH₂— — −65.38 344(M + 1) 29 CH₂═CHCH₂ NH —OCH₂CH₂CH₂— — −65.39 356 (M + 1) 30 CH≡CCH₂ NH—OCH₂CH₂CH₂— — −65.39 354 (M + 1) 31 CH₃ NH —OCH₂CH₂CH₂— — −65.44 330(M + 1) 32 CH≡CCH₂ N(Me) —OCH₂— — −65.36 340 (M + 1) 33 CH≡CCH₂CH₂ NH—OCH₂— — −65.40 340 (M + 1) 34 3-pyridinyl NH —OCH₂CH₂— — −65.36 379(M + 1) 35 3-pyridinyl NH —OCH₂CH₂CH₂— — −65.40 393 (M + 1) 36 CH₃C≡CCH₂NH —OCH₂— — −65.42 340 (M + 1) 41 H NH —OCH₂CH₂— — −64.72^(a) 42 CH₃ NH—OCH₂CH₂— — −65.37 43 (Ex. 2) CH₃CH₂ NH —OCH₂CH₂— — −65.39 44 CH₃ N(Me)—OCH₂CH₂— — −65.39 45 CH≡CCH₂ NH —OCH₂CH₂— — −65.37 47 4-(MeOC(═O))Ph NH—OCH₂— — −65.34 422 (M − 1) 48 4-(MeOC(═O))Ph NH —OCH(Me)— — −65.34 436(M + 1) 49 4-(MeOC(═O))Ph NH —OCH₂CH₂— — −65.36 436 (M + 1) 504-(MeOC(═O))Ph NH —OCH₂CH₂CH₂— — −65.38 450 (M + 1) 51 CH₂═CHCH₂ NH—OCH₂— — −65.36 52 CH₃CH₂ N(Me) —OCH₂— — −65.36 53 CH₃CH₂ N(Et) —OCH₂— —−65.36 54 c-Pr NH —OCH₂— — −65.36 55 N≡CCH₂ NH —OCH₂— — −65.35 574-(EtOC(═O))Ph NH —OCH₂— — −65.35 434 (M − 1) 58 4-(EtOC(═O))Ph NH—OCH(Me)— — −65.36 448 (M − 1) 59 4-(EtOC(═O))Ph NH —OCH₂CH₂— — −65.37448 (M − 1) 60 4-(EtOC(═O))Ph NH —OCH₂CH₂CH₂— — −65.38 462 (M − 1) 62CH₃C≡CCH₂ NH —OCH(Me)— — −65.35 63 CH₃C≡CCH₂ NH —OCH₂CH₂— — −65.41 64CH₃C≡CCH₂ NH —OCH₂CH₂CH₂— — −65.44 65 CH≡CCH₂CH₂ NH —OCH₂CH₂CH₂— —−65.48 368 (M + 1) 66 CH≡CCH₂CH₂ NH —OCH₂CH₂— — −65.42 354 (M + 1) 67CH≡CCH₂CH₂ NH —OCH(Me)— — −65.39 68 4-(EtOC(═O))PhCH₂ NH —OCH₂CH₂— —−65.37 464 (M + 1) 69 4-(EtOC(═O))PhCH₂ NH —OCH₂CH₂CH₂— — −65.38 478(M + 1) 71 CH₃ NH —OCH(Me)— — −65.35 72 CH₃ N(Me) —OCH(Me)— — −65.61 73CH₃CH₂CH₂ NH —OCH(Me)— — −65.33 65-67 75 CH₃CH₂ NH OCH(CH₂OMe)CH₂ —−65.39 76 CH≡CCH₂ NH —OCH(Me)— — −65.43 77 c-Pr NH —OCH(Me)— — −65.3790-92 342 (M + 1) 78 CH₃CH₂OC(═O) NH —OCH₂CH₂— — −65.35 79 CH₃CH₂OC(═O)NH —OCH₂— — −65.35 84 H NH —OCH(Me)— — −65.35 85 H NH —OCH₂— 3-F −65.33,−115.99 86 H NH —OCH₂— 3-Cl −65.33 87 H NH —OC(Me)₂— — −65.34 89 H NH—OCH₂— 2-F −65.21, 149-150 −106.66 90 H NH —OCH₂— 3-Me −65.35 108-109105 (Ex. 5) CH₃ O —NHN═CH— — −65.34 183-185 315 (M + 1) 106 t-Bu O—NHN═CH— — −65.35 356 (M − 1) 107 CH₃CH₂ O —NHN═CH— — −65.34 329 (M + 1)108 CH₃ O —NHN═C(Me)— — −65.35 329 (M + 1) 109 t-Bu O —N(Me)N═CH— —−65.36 136 H N(OMe) —OCH₂— — −65.34 316 (M − 1) ^(a19)F NMR in DMSO-d₆solution.

INDEX TABLE B

A dash “—” in the R¹³ column means that no R¹³ substituent is presentand the remaining carbon valences are occupied by hydrogen atoms. Cmpd.R¹ Z¹ R¹³ ¹⁹F NMR MS 101 H NH 3-Cl  −65.33 102 CH₃ NH 3-C1  −65.34 103CH₃CH₂ NH 3-Cl  −65.35 104 CH≡CCH₂ NH 3-Cl  −65.34 110 CH₃CH₂ NH — −65.35 112 H NH 4-F  −65.34, 381 (M − 1) −113.6 113 CH₃ NH 4-F  −65.34,395 (M − 1) −113.64 114 CH₃CH₂ NH 4-F  −65.35, 409 (M − 1) −113.69 115CH≡CCH₂ NH 4-F  −65.34, 381 (M − 1) −113.38 116 CH₃CH₂CH₂ NH 4-F −65.35, 321 (M + 1) −113.69 117 H NH —  −65.35 362 (M − 1) 118 CH≡CCH₂NH —  −65.35 400 (M − 1) 119 4-(MeOC(═O)) NH —  −65.35 511 (M − 1) PhCH₂120 CH≡CCH₂CH₂ NH —  −65.35 414 (M − 1) 121 CH₃ N(Me) —  −65.35 122CH₃OCH₂CH₂ NH —  −65.35 128 H NH 2-CH₃  −65.35 129 CH₃ NH 2-CH₃  −65.35130 CH₃CH₂ NH 2-CH₃  −65.35 317 (M − 1) 131 H NH 3-F  −65.34, 380 (M− 1) −112.10 132 CH₃ NH 3-F  −65.34, −112.21 133 CH₃CH₂ NH 3-F  −65.35,−112.22 134 CH₃ N(Me) 3-F  −65.35, −112.22 135 CH≡CCH₂ NH 3-F  −65.34,418 (M − 1) −112.05 137 CH₃ NH —  −65.35 138 CH₂═CHCH₂ NH —  −65.35 139CH₃CH₂CH₂ NH —  −65.35 140 (CH₃)₂CHCH₂ NH —  −65.35 143 H NH 4-CH₃ −65.35 144 CH₃ NH 4-CH₃  −65.35 145 CH₃CH₂ NH 4-CH₃  −65.35 146CH₂═C(Me)CH₂ NH 4-CH₃  −65.35

INDEX TABLE C

Cmpd. Z² ¹⁹F NMR MS  8 —OCH₂— −65.33 21 —OCH₂CH₂CH₂— −65.34 365 (M − 1)40 —OCH₂CH₂— −65.38 (Ex. 1) 70 —OCH(Me)— −65.32 351 (M − 1)

INDEX TABLE D

A dash “—” in the R¹³ column means that no R¹³ substituent is presentand the remaining carbon valences are occupied by hydrogen atoms. Cmpd.R¹³ ¹⁹F NMR MS  83 4-CH₃O  −65.41 100 4-CH₃  −65.37 111 —  −65.33 414 (M− 1) 127 4-F  −65.31, 431 (M − 1) −111.68 142 2-CH₃  −65.33 427 (M − 1)125 3-F  −65.32, 431 (M − 1) −111.12 126 3-Cl  −65.31 447 (M − 1)

INDEX TABLE E

Cmpd. R¹ Z¹ Z² A ¹⁹F NMR 37 CH≡CCH₂ NH —OCH₂— S −65.42 38 CH₃ NH —OCH₂—S −65.41 39 CH₃CH₂ NH —OCH₂— S −65.40 46 CH₃CH₂CH₂ NH —OCH₂— S −65.39 61CH≡CCH₂ NH —OCH(Me)— S −65.43 74 CH₃CH₂CH₂ NH —OCH(Me)— S −65.41 80 H NH—OCH₂— O −65.30 81 CH≡CCH₂ NH —OCH₂— O −65.31 124 CH₃CH₂ O —NHN═CH— S−65.39 141 CH₃ O —NHN═CH— S −65.39

INDEX TABLE F

Cmpd. R¹ Z¹ Z² ¹⁹F NMR 93 H NH —OCH₂— −65.37 94 CH₃ NH —OCH₂— −65.35 95CH₃CH₂ NH —OCH₂— −65.37 96 CH≡CCH₂ NH —OCH₂— −65.36 97 CH₂═CHCH₂ NH—OCH₂— −65.36 98 CH₂═C(Me)CH₂ NH —OCH₂— −65.34 99 CH₃ N(Me) —OCH₂—−65.37

INDEX TABLE G

Cmpd. R¹—Z¹—C(═W)—Z²—J— ¹⁹F NMR M.P. 18

−65.44 82

−65.27 88

−65.18 159-160 91

−65.35 107-108 123

−65.32

BIOLOGICAL EXAMPLES OF THE INVENTION

General protocol for preparing test suspensions for Tests A-C: the testcompounds were first dissolved in acetone in an amount equal to 3% ofthe final volume and then suspended at the desired concentration (inppm) in acetone and purified water (50/50 mix by volume) containing 250ppm of the surfactant PEG400 (polyhydric alcohol esters). The resultingtest suspensions were then used in Tests A-C.

Test A

The test solution was sprayed to the point of run-off on soybeanseedlings. The following day the seedlings were inoculated with a sporesuspension of Phakopsora pachyrhizi (the causal agent of Asian soybeanrust) and incubated in a saturated atmosphere at 22° C. for 24 h, andthen moved to a growth chamber at 22° C. for 8 days, after which timevisual disease ratings were made.

Test B

The test solution was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Zymoseptoria tritici (the causal agent of wheat leafblotch) and incubated in a saturated atmosphere at 24° C. for 48 h, andthen moved to a growth chamber at 20° C. for 17 days, after which timedisease ratings were made.

Test C

The test solution was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Puccinia recondita f. sp. tritici (the causal agent ofwheat leaf rust) and incubated in a saturated atmosphere at 20° C. for24 h, and then moved to a growth chamber at 20° C. for 6 days, afterwhich time disease ratings were made.

Results for Tests A-C are given in Table A. In the Table, a rating of100 indicates 100% disease control and a rating of 0 indicates nodisease control (relative to the controls). A dash (-) indicates thecompound was not tested.

TABLE A Cmpd No. Rate in ppm Test A Test B Test C 1 270 100 79 100 2 260100 99 100 3 250 100 73 100 4 260 100 46 100 5 260 100 81 100 6 260 10076 100 7 260 100 98 100 8 255 100 13 100 9 260 100 94 100 10 250 100 97100 11 250 100 96 100 12 265 100 100  100 13 260 100 36 100 14 250 10084 100 15 265 100 92 100 16 255 100 19 100 17 260 100 92 100 18 50 38 50* 0 19 10 100 — 74 20 10 100 — 99 21 50 100 — 99 22 10 99 — 97 23 10100 — 97 24 10 13 — 68 25 10 100 — 26 26 10 95 — 26 27 10 100 — 0 28 10100 — 40 29 10 100 — 74 30 10 100 — 99 31 10 100 — 99 32 10 100  0* 6833 10 100  0* 100 34 50 100 — 98 35 50 100 — 100 36 10 100 — 100 37 50100 — 100 38 10 94  80* 96 39 10 96  93* 95 40 10 0 — 18 41 10 100 — 9942 10 100  0 99 43 10 100  0* 97 44 10 100 — 41 45 10 100 — 93 46 10 99 97* 97 47 50 100 — 41 48 50 100 — 97 49 50 96 — 0 50 50 0 — 0 51 10 100— 99 52 10 100 — 68 53 10 100 — 68 54 10 100 — 92 55 10 100 — 86 57 10100 — 0 58 50 100 — 79 59 50 96 — 0 60 50 0 — 0 61 10 100 — 100 62 50100 — 100 63 50 100 — 100 64 50 100 — 100 65 50 100 — 100 66 50 100 —100 67 50 100 — 100 68 50 99 — 0 69 50 100 — 0 70 10 99 — 68 71 10 100 —83 72 10 100  0* 55 73 10 100 — 68 74 10 100 — 98 75 10 100  97* 91 7610 100  0* 99 77 10 100  0 92 78 10 100 95 91 79 10 100 98 97 80 10 0 —0 81 10 0 — 45 82 50 89 — 0 83 50 100 — 100 84 10 100 — 100 85 250 10098 100 86 250 100 94 100 87 250 100 99 100 88 — — — — 89 — — — — 90 — —— — 91 — — — — 93 250 100 97 100 94 250 69  1 100 95 250 99  3 100 96250 100 64 100 97 250 100 52 100 98 250 100  3 100 99 250 0  0 55 100250 100 98 97 101 250 100 90 99 102 250 100 96 90 103 250 100 20 86 104250 100 84 80 105 250 100 99 100 106 10 97 — 68 107 10 100 — 99 108 1092 — 89 109 50 100 — 95 110 250 100 — 100 111 250 100 — 100 112 250 10085 100 113 250 100 82 100 114 250 100  9 100 115 250 100 66 100 116 250100  0 88 117 250 100 — 100 118 250 100 — 100 119 250 100 — 74 120 250100 — 100 121 250 100 — 99 122 10 100 — 89 123 250 100  0 96 124 50 100 73* 100 125 250 100 97 100 126 10 99  88* 0 127 250 100 99 100 128 250100 88 100 129 250 100 74 100 130 250 100  3 98 131 250 100 96 100 132250 100 95 100 133 250 100 99 100 134 250 100 50 89 135 250 100 88 100136 10 79 — 0 137 250 100 70 100 138 250 100 99 100 139 250 100 56 100140 250 100 34 86 141 50 100  93* 100 142 10 98 — 0 143 250 100 69 100144 250 100  0 100 145 250 100 28 98 146 250 100 21 97 *Indicatescompound was tested at 250 ppm.

What is claimed is:
 1. A compound selected from Formula 1, N-oxides, andsalts thereof,

wherein R¹ is H, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₂-C₄alkylcarbonyl or C₂-C₄ alkoxycarbonyl; or U-50

wherein R³ is selected from R^(3a); and k is 0, 1 or 2; Z¹ is—(CH₂)_(n)NR^(4a), wherein the bond projecting to the left is attachedto R¹, and the bond projecting to the right is attached to C=W; W is Oor S; Z² is —O(CH₂)m-, —OCH₂CH₂O- or —NR⁵N═CH-, wherein the bondprojecting to the left is attached to C=W, and the bond projecting tothe right is attached to J; J is

wherein the bond projecting to the left is bonded to Z², and the bondprojecting to the right is bonded to the oxadiazole ring in Formula 1;and each R^(7a)is H; each R^(3a) is independently methyl, C₂-C₄alkylcarbonyl or C₂-C₄ alkoxycarbonyl; R^(4a) is H; R⁵ is H; n is 0; andm is 1,2 or 3; provided that: (b) the compound of Formula 1 is not:[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methylN-methylcarbamate;[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methylN-ethylcarbamate;[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methylN-propylcarbamate;[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methylN-(1-methylethyl)carbamate;[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methylN-(2-methylpropyl)carbamate; and[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methylN-butylcarbamate.
 2. A compound of claim 1 wherein: Z² is —O(CH₂)_(m)—;W is O; J is J-50; and m is 1 or
 2. 3. A compound which is selected fromthe group: [4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl]phenyl]methylcarbamate (Compound 17); 2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]ethyl N-ethylcarbamate (Compound 43); and methyl2-[[4-[5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl]phenyl]methylene]-hydrazinecarboxylate (Compound 105).


4. A fungicidal composition comprising (a) a compound of claim 1; and(b) at least one other fungicide.
 5. A fungicidal composition comprising(a) a compound of claim 1; and (b) at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents.
 6. A method for controlling plant diseases caused byfungal plant pathogens comprising applying to the plant or portionthereof, or to the plant seed, a fungicidally effective amount of acompound of claim
 1. 7. A method for controlling plant diseases causedby Basidiomycetes fungal plant pathogens comprising applying to theplant or portion thereof, or to the plant seed, a fungicidally effectiveamount of a compound of claim
 1. 8. A compound of claim 1 which isselected from:

wherein R¹ is CH≡CCH₂ and Z² is OCH₂; or R¹ is H and Z² is OCH₂; or R¹isCH≡CCH₂CH₂ and Z² is OCH₂; or R¹ is CH₃CCCH₂ and Z² is OCH₂; or R¹is Hand Z² is OCH₂CH₂; or R¹is CH₃ and Z² is OCH₂CH₂; or R¹is CH₃CH₂ and Z²is OCH₂CH₂; or R¹is CH≡CCH₂ and Z² is OCH₂CH₂; or R¹is CH₂=CHCH₂ and Z²is OCH₂; or R¹ is CH₃C≡CCH₂ and Z² is OCH₂CH₂; or R¹ is CH₃C≡CCH₂ and Z²is OCH₂CH₂CH₂; or R¹ is CH≡CCH₂CH₂ and Z² is OCH₂CH₂CH₂; or R¹ isCH≡CCH₂CH₂ and Z² is OCH₂CH₂; or R¹ is CH₃CH₂OC(=O) and Z² is OCH₂CH₂;or R¹ is CH₃CH₂OC(=O) and Z² is OCH₂.
 9. A compound of claim 1 which isselected from:

wherein R¹ is CH₃, CH₃CH₂, CH₃CH₂CH₂ or CH≡CCH₂.